Herbicidal agents based on pyrazole derivatives

ABSTRACT

Herbicidally active 5-amino-1-phenyl-pyrazoles, most of which are new, of the formula ##STR1##

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation, of application Ser. No. 298,880,filed Jan. 18, 1989, now abandoned, which is a continuation ofapplication Ser. No. 887,290 filed Jul. 21, 1986, now abandoned, whichis a continuation-in-part of application Ser. No. 785,927, filed Oct. 9,1985, now abandoned, which in turn was a division of application Ser.No. 690,347, filed Jan. 10, 1985, now U.S. Pat. No. 4,614,533.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the use of 5-amino-1-phenyl-pyrazoles,some of which are known, as herbicides.

2. Background Information

It is known that certain 5-amino-1-phenyl-pyrazoles which aresubstituted in the 4-position by a cyano group, such as, for example,4-cyano-5-propionylamino-1-(2,4,6-trichlorophenyl)-pyrazole, possessherbicidal properties (see, for example, European Patent 34,945).

However, their herbicidal activity against some problem weeds, liketheir compatibility with important crop plants, is not always completelysatisfactory in all fields of use.

5-Amino-1-phenylpyrazoles which are unsubstituted in the 4-position orsubstituted in the 4-position by methyl or phenyl, such as, for example5-amino-1-(2,4-dinitrophenyl)-4-methylpyrazole,5-amino-1-(2,4-dinitrophenyl)-4-phenylpyrazole,5-amino-4-(4-chlorophenyl)-1-(2,4-dinitrophenyl)-pyrazole,5-amino-1-(2,4-dinitrophenyl)-4-(4-methoxyphenyl)-pyrazole or5-acetamido-1-(2,4,6-trinitrophenyl)-pyrazole, are also known (see J.Org. Chemistry 36, 2972-2974 [1971]; J. Heterocycl. Chem. 7, 345-349[1970] and C.A. 62, 13137c). However, nothing is known about theiractivity as herbicides.

SUMMARY OF THE INVENTION

It has been found that the substituted 5-amino-1-phenyl-pyrazoles, someof which are known, of the general formula (I) ##STR2## in which R¹represents hydrogen, nitroso, nitro, halogen, alkyl, halogenoalkyl,optionally substituted aryl or one of the radicals ##STR3## R²represents hydrogen or a radical ##STR4## R³ independently of R²represents the same radicals as R² and additionally represents alkyl,

R⁴ and R⁶ independently of one another represent cyano, nitro, halogen,alkyl, alkoxy, alkoxy carbonyl, halogenoalkyl, halogenoalkoxy or aradical --S(O)_(n) --R¹³, and

R⁵, R⁷ and R⁸ independently of one another and of R⁴ and R⁶ representthe same radicals as R⁴ and R⁶ and additionally represent hydrogen, and

R⁹ represents hydrogen, hydroxyl, halogen, amino, alkylamino,dialkylamino, alkyl, halogenoalkyl or optionally substituted aryl,

R¹⁰ represents hydrogen, alkyl or optionally substituted aryl,

R¹¹ represents hydrogen, alkyl, halogenoalkyl, alkenyl, alkinyl oraralkyl,

R¹² represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl,alkoxyalkyl, alkylthioalkyl, optionally substituted cycloalkyl,optionally substituted aryl, alkoxy, alkylthio, optionally substitutedaryloxy, optionally substituted arylthio, alkylamino, dialkylamino oroptionally substituted arylamino,

R¹³ represents alkyl, halogenoalkyl, amino, alkylamino or dialkylamino,

X represents oxygen or sulphur, and

n represents the numbers 0, 1 or 2, possess herbicidal properties, inparticular selective herbicidal properties.

Surprisingly, the substituted 5-amino-1-phenylpyrazoles of the formula(I) which are to be used according to the invention exhibit, in additionto an improved herbicidal action against certain weeds, substantiallyimproved compatibility with important crop plants compared with the4-cyano-5-amino-1-phenylpyrazoles known from the prior art, such as, forexample, 4-cyano-5-propionylamino-1-(2,4,6-trichlorophenyl)-pyrazole,which is a similar compound chemically and in terms of its action.

The substituted 5-amino-1-phenyl-pyrazoles to be used according to theinvention thus represent an enrichment of the art.

Formula (I) gives a general definition of the substituted5-amino-1-phenyl-pyrazoles to be used according to the invention.Preferred compounds of the formula (I) are those in which

R¹ represents hydrogen, nitroso, nitro, halogen, alkyl or halogenoalkyl,each of which is straight-chain or branched and each of which has up to6 carbon atoms and, in the case of halogenoalkyl, up to 9 identical ordifferent halogen atoms, or represents phenyl which is optionallymonosubstituted or polysubstituted by identical or differentsubstituents from amongst halogen, nitro, alkyl, alkoxy orhalogenoalkyl, each having up to 4 carbon atoms, or represents one ofthe radicals ##STR5## R² represents hydrogen or a radical ##STR6## R³independently of R² represents the same radicals as R², and additionallyrepresents straight-chain or branched alkyl having up to 4 carbon atoms,

R⁴ and R⁶ independently of one another represent cyano, nitro, halogen,or alkyl, alkoxy or alkoxy-carbonyl, each of which is straight-chain orbranched and each of which has up to 4 carbon atoms, and furthermorerepresents halogenoalkyl or halogenoalkoxy, each of which isstraight-chain or branched and each of which has up to 4 carbon atomsand up to 9 identical or different halogen atoms, or represents aradical --S(O)_(n) --R¹³, and

R⁵, R⁷ and R⁸ independently of one another and of R⁴ and R⁶ representthe same radicals as R⁴ and R⁶ and additionally represent hydrogen and

R⁹ represents hydrogen, hydroxyl, fluorine, chlorine, bromine, amino oralkylamino, dialkylamino, alkyl or halogenoalkyl, each of which isstraight-chain or branched and each of which has up to 4 carbon atoms inthe individual alkyl parts, and, in the case of halogenoalkyl, up to 9identical or different halogen atoms, and represents phenyl which isoptionally monosubstituted or polysubstituted by identical or differentsubstituents, the following being suitable substituents: halogen, alkyl,alkoxy or halogenoalkyl, each of which is straight-chain or branched andeach of which has up to 4 carbon atoms and, in the case ofhalogenoalkyl, up to 9 identical or different halogen atoms,

R¹⁰ represents hydrogen, straight-chain or branched alkyl having up to 4carbon atoms, or phenyl which is optionally monosubstituted orpolysubstituted by identical or different substituents, suitable phenylsubstituents being those mentioned in the case of R⁹,

R¹¹ represents hydrogen, halogenoalkyl having up to 4 carbon atoms andup to 6 identical or different halogen atoms, alkyl, alkenyl or alkinyl,each of which is straight-chain or branched and each of which has up to8 carbon atoms, and straight-chain or branched phenylalkyl having up to4 carbon atoms in the alkyl part,

R¹² represents hydrogen, or alkyl which is straight-chain or branchedand which has 1 to 12 carbon atoms, or alkenyl, alkinyl, alkoxyalkyl,alkylthioalkyl, alkoxy, alkylthio, alkylamino, dialkylamino orhalogenoalkyl, each of which is straight-chain or branched and each ofwhich has up to 4 carbon atoms in the individual alkyl parts and, in thecase of halogenoalkyl, up to 9 identical or different halogen atoms, andfurthermore represents cycloalkyl which has 3 to 7 carbon atoms and isoptionally monosubstituted or polysubstituted by identical or differentsubstituents from amongst halogen, lower alkyl or lower halogenoalkyl,and represents phenyl, phenoxy, phenylthio or phenylamino, each of whichis optionally monosubstituted or polysubstituted by identical ordifferent substituents, suitable phenyl substituents being those statedin the case of R⁹ ;

R¹³ represents amino, and alkyl, alkylamino, dialkylamino orhalogenoalkyl, each of which is straight-chain or branched and each ofwhich has up to 4 carbon atoms in the individual alkyl parts and, in thecase of halogenoalkyl, up to 9 identical or different halogen atoms,

X represents oxygen or sulphur and

n represents the number 0, 1 or 2.

Particularly preferred compounds of the formula (I) are those in which:

R¹ represents hydrogen, nitroso, nitro, fluorine, chlorine, bromine,methyl, ethyl, n- and i-propyl, n-, i, s- and t-butyl, trifluoromethyl,or phenyl which is optionally monosubstituted to trisubstituted byidentical or different substituents from amongst fluorine, chlorine,bromine, nitro, methyl, ethyl, methoxy and trifluoromethyl, orrepresents one of the radicals ##STR7## R² represents hydrogen or aradical ##STR8## R³ independently of R² represents the same radicals asR² and additionally represents methyl, ethyl, n- and i-propyl, n-, i-,s- and t-butyl,

R⁴ and R⁶ independently of one another represent cyano, nitro, fluorine,chlorine, bromine, iodine, methyl, ethyl, n- and i-propyl, n-, i-, s-and t-butyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl,trifluoromethyl, trichloromethyl, dichlorofluoromethyl,difluorochloromethyl, chloromethyl, dichloromethyl, difluoromethyl,pentafluoroethyl, tetrafluoroethyl, trifluorochloroethyl,trifluoroethyl, difluorodichloroethyl, trifluorodichloroethyl,pentachloroethyl, trifluoromethoxy, trichloromethoxy,dichlorofluoromethoxy, difluorochloromethoxy, chloromethoxy,dichloromethoxy, difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy,trifluorochloroethoxy, trifluoroethoxy, difluorodichloroethoxy,trifluorodichloroethoxy, pentachloroethoxy or a radical --S(O)_(n)--R¹², and

R⁵, R⁷ and R⁸ independently of one another and of

R⁴ and R⁶ represent the same radicals as R⁴ and R⁶ and additionallyrepresent hydrogen, and

R⁹ represents hydrogen, hydroxyl, fluorine, chlorine, bromine, amino,methylamino, dimethylamino, ethylamino, diethylamino, diisopropylamino,di-n-butylamino, methyl, ethyl, dichlorofluoromethyl or trifluoromethyl,and represents phenyl which is optionally monosubstituted totrisubstituted by identical or different substituents from amongstmethyl, methoxy, trifluoromethyl and chlorine,

R¹⁰ represents hydrogen, methyl, ethyl, n- and i-propyl, and representsphenyl which is optionally monosubstituted to trisubstituted byidentical or different substituents from amongst methyl, methoxy,trifluoromethyl and chlorine,

R¹¹ represents hydrogen, methyl, ethyl, n- and i-propyl, n-, i-, s- andt-butyl, alkyl, butenyl, propargyl, benzyl, chloroethyl or bromoethyl,

R¹² represents hydrogen, methyl, ethyl, n- and i-propyl, undecyl, vinyl,allyl, propargyl, butenyl, methoxymethyl, ethoxymethyl, methoxyethyl,ethoxyethyl, methylthiomethyl, methoxy, ethoxy, methylthio, ethylthio,methylamino, ethylamino, dimethylamino, diethylamino, trifluoromethyl,trichloroethyl, dichlorofluoroethyl, difluorochloroethyl, chloromethyl,iodomethyl, bromomethyl, dichloromethyl, 1-chloroethyl, 2-chloroethyl,2-bromoethyl, chloropropyl or heptafluoron-propyl, or representscyclopentyl, cyclohexyl or cyclopropyl which is optionallymonosubstituted to tetrasubstituted by identical or differentsubstituents from amongst fluorine, chlorine, bromine, methyl andtrifluoromethyl, and represents phenyl, phenoxy, phenylthio orphenylamino, each of which is optionally monosubstituted totrisubstituted by identical or different substituents from amongstmethyl, methoxy, chlorine and trifluoromethyl,

R¹³ represents amino, methylamino, ethylamino, dimethylamino,diethylamino, fluorodichloromethyl, difluoromethyl, tetrafluoroethyl,trifluorochloroethyl, trifluoromethyl, methyl or ethyl,

X represents oxygen or sulphur, and

n represents the number 0, 1 or 2.

DETAILED DESCRIPTION OF THE INVENTION

In addition to the compounds mentioned in the preparation examples, thefollowing 5-amino-1-phenyl-pyrazoles of the general formula (I) may bementioned individually: ##STR9##

                                      TABLE 1                                     __________________________________________________________________________    R.sup.1   R.sup.2       R.sup.3                                                                            R.sup.4                                                                          R.sup.5                                                                         R.sup.6                                                                              R.sup.7                                                                         R.sup.8                            __________________________________________________________________________    H         CH.sub.3 CO   H    Cl H Cl     H H                                  H         CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H Cl     H H                                  H         CH.sub.3 CO   H    Cl H Cl     H Cl                                 H         CH.sub.3 CO   CH.sub.3                                                                           Cl H Cl     H Cl                                 H         CH.sub.3 CO   H    NO.sub.2                                                                         H NO.sub.2                                                                             H H                                  H         H             H    Cl H CF.sub.3                                                                             H Cl                                 H         CH.sub.3 CO   H    Cl H OCF.sub.3                                                                            H H                                  H         C.sub.2 H.sub.5 CO                                                                          H    CF.sub.3                                                                         H SCF.sub.3                                                                            H H                                  H         C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     H H                                  H         H             H    Cl Cl                                                                              Cl     H H                                  H         CH.sub.3 CO   CH.sub.3 CO                                                                        Cl Cl                                                                              Cl     H H                                  H         CH.sub.3 CO   C.sub.2 H.sub.5 CO                                                                 Cl Cl                                                                              Cl     H H                                  H         C.sub.2 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H Cl                                 H         CH.sub.3 CO   H    Cl H CF.sub.3                                                                             H Cl                                                         H    Cl H CF.sub.3                                                                             H Cl                                 H         CH.sub.3 OCO  H    Cl H CF.sub.3                                                                             H Cl                                 H         n-C.sub.3 H.sub.7 CO                                                                        H    Cl H CF.sub.3                                                                             H Cl                                 H         CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H CF.sub.3                                                                             H Cl                                 H         C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.3                                                                            H H                                  H                                                                                        ##STR10##    H    Cl H OCF.sub.3                                                                            H H                                  H         n-C.sub.4 H.sub.9CO                                                                         H    Cl H OCF.sub.3                                                                            H H                                  H         C.sub.2 H.sub.5 CO                                                                          H    Cl H SCF.sub.3                                                                            H Cl                                 H         n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SCF.sub.3                                                                            H Cl                                 H                                                                                        ##STR11##    H    Cl H SCF.sub.3                                                                            H Cl                                 H         CH.sub.3 CO   H    Cl H SCF.sub.3                                                                            H Cl                                 H         CH.sub.3 OCO  H    Cl H SCF.sub.3                                                                            H Cl                                 H         CH.sub.3 OCO  H    Cl H OCF.sub.3                                                                            H H                                  H         C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     H Cl                                 H         CH.sub.3 CO   H    Cl Cl                                                                              Cl     H Cl                                 H         CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  H                                                                                        ##STR12##    H    Cl Cl                                                                              Cl     H Cl                                 H         CH.sub.3 OCO  H    Cl Cl                                                                              Cl     H Cl                                 H         CH.sub.3 CO   H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 H         C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 H         n-C.sub.3 H.sub.7 CO                                                                        H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 H                                                                                        ##STR13##    H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 H         CH.sub.3 OCO  H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 H         CONHCH.sub.3  H    Cl Cl                                                                              Cl     H H                                  H         CONHCH.sub.3  H    Cl H CF.sub.3                                                                             H Cl                                 H         CH.sub.3 CO   H    Cl Cl                                                                              SCF.sub.3                                                                            H H                                  H         CH.sub.3 CO   H    F  F OCF.sub.3                                                                            H F                                  H         C.sub.2 H.sub.5 CO                                                                          CH.sub.3 CO                                                                        F  F OCF.sub.3                                                                            F F                                  Cl        H             H    Cl Cl                                                                              Cl     H H                                  Cl        H             H    Cl H Cl     H H                                  Cl        H             H    Cl H CF.sub.3                                                                             H Cl                                 Cl        H             H    Cl H SCF.sub.3                                                                            H Cl                                 Cl        CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  Cl        CH.sub.3 CO   H    Cl Cl                                                                              OCF.sub.3                                                                            H H                                  Cl        CH.sub.3 CO   CH.sub.3                                                                           Cl Cl                                                                              SCF.sub.3                                                                            H H                                  Cl        C.sub.2 H.sub.5 CO                                                                          H    F  F OCF.sub.3                                                                            F F                                  Cl        C.sub.2 H.sub.5 CO                                                                          H    Br H SCF.sub.3                                                                            H H                                  Cl        C.sub.2 H.sub.5 CO                                                                          H    Cl H SCF.sub.3                                                                            H Cl                                 Cl        C.sub.2 H.sub.5 CO                                                                          CH.sub.3 CO                                                                        Cl Cl                                                                              SCF.sub.3                                                                            H H                                  Cl        CH.sub.3 CO   CH.sub.3 CO                                                                        Cl Cl                                                                              Cl     H H                                  Cl        CH.sub.3 CO   C.sub.2 H.sub.5 CO                                                                 Cl Cl                                                                              Cl     H H                                  Cl        CONHCH.sub.3  H    Cl Cl                                                                              OCF.sub.3                                                                            H H                                  Cl        COOC.sub.2 H.sub.5                                                                          H    Br H OCF.sub.3                                                                            H Br                                 Cl        COC.sub.6 H.sub.5                                                                           H    NO.sub.2                                                                         H NO.sub.2                                                                             H NO.sub.2                           Cl        COCF.sub.3    H    NO.sub.2                                                                         H NO.sub.2                                                                             H H                                  Br        CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  Br        CH.sub.3 OCH.sub.2 CO                                                                       H    Cl H Cl     H Cl                                 Br        CH.sub.3 SCH.sub.2CO                                                                        H    NO.sub.2                                                                         H NO.sub.2                                                                             H H                                  Br        CH.sub.3 CO   CH.sub.3 CO                                                                        Cl Cl                                                                              CF.sub.3                                                                             H H                                  Br        C.sub.2 H.sub.5 CO                                                                          CH.sub.3 CO                                                                        Cl H CF.sub.3                                                                             H Cl                                 Br        CH.sub.3 CO   H    Cl H OCF.sub.3                                                                            H Cl                                 Br                                                                                       ##STR14##    H    F  H OCF.sub.3                                                                            H F                                  Br                                                                                       ##STR15##    H    F  F OCF.sub.3                                                                            H F                                  Br                                                                                       ##STR16##    H    F  F SCF.sub.3                                                                            H F                                  Br        H             H    F  H SCF.sub.3                                                                            H F                                  Br        C.sub.2 H.sub.5 CO                                                                          H    Cl H Cl     H Cl                                 Br                                                                                       ##STR17##    H    Cl H Cl     H H                                  Br                                                                                       ##STR18##    H    Cl Cl                                                                              Cl     H H                                  Br        CH.sub.3 CO   CH.sub.3                                                                           Cl H SO.sub. 2 CF.sub.3                                                                   H Cl                                 Br        F.sub.3 CCO   H    Cl H SOCF.sub.3                                                                           H Cl                                 Br        ClCH.sub.2 CO H    CF.sub.3                                                                         H CF.sub.3                                                                             H CF.sub.3                           Br        Cl.sub.2 CHCO H    CF.sub.3                                                                         H SO.sub.2 CF.sub.3                                                                    H CF.sub.3                           I         H             H    Cl Cl                                                                              Cl     H H                                  I         H             H    Cl H Cl     H Cl                                 I         H             H    Cl H CF.sub.3                                                                             H Cl                                 I         CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  I         CH.sub.3 CO   H    Cl H CF.sub.3                                                                             H Cl                                 I         CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H OCF.sub.3                                                                            H Cl                                 I         CH.sub.3 CO   CH.sub.3 CO                                                                        CF.sub.3                                                                         H SCF.sub.3                                                                            H CF.sub.3                           I         C.sub.2 H.sub.5 CO                                                                          H    CF.sub.3                                                                         H SCF.sub.3                                                                            H H                                  I         C.sub.2 H.sub.5 CO                                                                          CH.sub.3 CO                                                                        Br H CF.sub.3                                                                             H Br                                 I         C.sub.2 H.sub.5 CO                                                                          CH.sub.3                                                                           Cl Cl                                                                              Cl     H H                                  I         C.sub.6 H.sub.5 CO                                                                          H    F  F OCF.sub.3                                                                            F F                                  I                                                                                        ##STR19##    H    Cl H OCF.sub.3                                                                            H Cl                                 I         F.sub.3 C CO  H    F  H OCF.sub.3                                                                            H F                                  I         ClCH.sub.2 CO H    Cl H SCF.sub.3                                                                            H Cl                                 I         Cl.sub.2 CHCO H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 I                                                                                        ##STR20##    H    F  F SO.sub.2 CF.sub.3                                                                    F F                                  I                                                                                        ##STR21##    H    Cl Cl                                                                              Cl     H H                                  CF.sub.3  H             H    Cl H Cl     H Cl                                 CF.sub.3  H             H    NO.sub.2                                                                         H NO.sub.2                                                                             H NO.sub.2                           CF.sub.3  CH.sub.3 CO   H    Cl H CF.sub.3                                                                             H Cl                                 CF.sub.3  CH.sub.3 CO   H    Cl H OCF.sub.3                                                                            H Cl                                 CF.sub.3  CH.sub.3 CO   CH.sub.3                                                                           Cl Cl                                                                              CF.sub.3                                                                             H H                                  CF.sub.3  CH.sub.3 CO   CH.sub.3 CO                                                                        Cl Cl                                                                              Cl     H H                                  CF.sub.3  C.sub.2 H.sub.5 CO                                                                          H    Cl H SCF.sub.3                                                                            H Cl                                 CF.sub.3  C.sub.2 H.sub.5 CO                                                                          H    F  F SCF.sub.3                                                                            H F                                  CF.sub.3  C.sub.2 H.sub.5 CO                                                                          CH.sub.3 CO                                                                        F  F OCF.sub.3                                                                            F F                                  CF.sub.3  H.sub.6 H.sub.5 CO                                                                          H    Cl Cl                                                                              SCF.sub.3                                                                            Cl                                                                              Cl                                 CF.sub.3  CH.sub.3 NHCO H    Cl H SO.sub.2 CH.sub.3                                                                    H Cl                                 CF.sub.3                                                                                 ##STR22##    H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 CF.sub.3                                                                                 ##STR23##    H    Cl Cl                                                                              Cl     H H                                  CF.sub.3                                                                                 ##STR24##    H    Cl H Cl     H Cl                                           Cl                                                                  CF.sub.3                                                                                 ##STR25##    H    Cl Cl                                                                              Cl     H H                                  CF.sub.3  C.sub.6 H.sub.5 OCO                                                                         H    CF.sub.3                                                                         H CF.sub.3                                                                             H H                                  CF.sub.3  C.sub.2 H.sub.5 OCO                                                                         H    Cl H CF.sub.3                                                                             H Cl                                 NO.sub.2  H             H    Cl Cl                                                                              Cl     H H                                  NO.sub.2  H             H    Cl F Cl     H Cl                                 NO.sub.2  H             H    Cl H CF.sub.3                                                                             H Cl                                 NO.sub.2  H             H    Cl H OCF.sub.3                                                                            H Cl                                 NO.sub.2  H             H    Cl H SCF.sub.3                                                                            H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  NO.sub.2  CH.sub.2 CO   H    Cl H CF.sub.3                                                                             H Cl                                 NO.sub.2  CH.sub.3 CO   H    CF.sub.3                                                                         H CF.sub.3                                                                             H CF.sub.3                           NO.sub.2  CH.sub.3 CO   CH.sub.3 CO                                                                        CF.sub.3                                                                         H CF.sub.3                                                                             H H                                  NO.sub.2  CH.sub.3 CO   CH.sub.3 CO                                                                        Cl Cl                                                                              Cl     H H                                  NO.sub.2  CH.sub.3 CO   CH.sub.3                                                                           Cl H Cl     H Cl                                 NO.sub.2  CH.sub.3 CO   CH.sub.3                                                                           CF.sub.3                                                                         H CF.sub.3                                                                             H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H Cl     H Cl                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          CH.sub.3 CO                                                                        Cl Cl                                                                              Cl     H H                                  NO.sub.2  C.sub.3 H.sub.5 CO                                                                          H    F  F F      F F                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    F  F CF.sub.3                                                                             F F                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     H H                                  NO.sub.2  C.sub.6 H.sub.5 CO                                                                          H    Cl H Cl     H H                                  NO.sub.2  CH.sub.3 NHCO H    Cl Cl                                                                              Cl     H H                                  NO.sub.2  CH.sub.3 NHCO CH.sub.3                                                                           Cl H Cl     H Cl                                 NO.sub.2  C.sub.6 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     Cl                                                                              Cl                                 NO.sub. 2                                                                                ##STR26##    H    F  F F      F F                                  NO.sub.2                                                                                 ##STR27##    H    F  H CF.sub.3                                                                             H F                                  NO.sub.2                                                                                 ##STR28##    H    Cl H CF.sub.3                                                                             H Cl                                 NO.sub.2  C.sub.2 H.sub.5 OCO                                                                         H    Cl Cl                                                                              CF.sub.3                                                                             H H                                  NO.sub.2  C.sub.2 H.sub.5 OCO                                                                         H    Cl H OCF.sub.3                                                                            H Cl                                 NO.sub.2  C.sub.6 H.sub.5 OCO                                                                         H    Cl H OCF.sub.3                                                                            H H                                  NO.sub.2  C.sub.6 H.sub.5 OCO                                                                         H    Cl Cl                                                                              Cl     H H                                  NO.sub.2                                                                                 ##STR29##    H    Cl H SO.sub.2 CH.sub.3                                                                    H Cl                                 NO.sub.2                                                                                 ##STR30##    H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO.sub.2  CH.sub.3 OCH.sub.2 CO                                                                       H    Cl Cl                                                                              Cl     H H                                  NO.sub.2  ClCH.sub.2 CO H    Cl H Cl     H H                                  NO.sub. 2 Cl.sub.2 CHCO H    Cl H Cl     H Cl                                 NO.sub.2  Cl.sub.2 CHCO H    Cl H CF.sub.3                                                                             H Cl                                 NO        H             H    Cl Cl                                                                              Cl     H H                                  NO        H             H    Cl H Cl     H Cl                                 NO        H             H    Cl H CF.sub.3                                                                             H Cl                                 NO        CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  NO        CH.sub.3 CO   H    Cl H Cl     H Cl                                 NO        CH.sub.3 CO   H    Cl H CF.sub.3                                                                             H Cl                                 NO        CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H OCF.sub.3                                                                            H Cl                                 NO        CH.sub.3 CO   CH.sub.3                                                                           Cl Cl                                                                              CF.sub.3                                                                             Cl                                                                              Cl                                 NO        CH.sub.3 CO   C.sub.2 H.sub.5 CO                                                                 F  H OCF.sub.3                                                                            H F                                  NO        C.sub.2 H.sub.5 CO                                                                          H    F  F OCF.sub.3                                                                            F F                                  NO        C.sub.2 H.sub.5 CO                                                                          H    F  F F      F F                                  NO        ClCH.sub.2 CO H    Cl H SO.sub.2 CH.sub.3                                                                    H Cl                                 NO        Cl.sub.2 CHCO H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO        CF.sub.3 CO   H    Cl Cl                                                                              SO.sub.2 CF.sub.3                                                                    H H                                  NO        CH.sub.3 NHCO H    Cl H Cl     H H                                  NO        C.sub.2 H.sub.5 OCO                                                                         H    Cl Cl                                                                              Cl     H H                                  NO        CF.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  NO        C.sub.6 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     H H                                  HCO       H             H    Cl Cl                                                                              Cl     H H                                  HCO       H             H    Cl H Cl     H Cl                                 HCO       H             H    Cl H CF.sub.3                                                                             H Cl                                 HCO       CH.sub.3 CO   H    Cl H CF.sub.3                                                                             H Cl                                 HCO       CH.sub.3 CO   H    Cl H OCF.sub.3                                                                            H Cl                                 HCO       CH.sub.3 CO   H    Cl H SCF.sub.3                                                                            H Cl                                 HCO       CH.sub.3 CO   CH.sub.3                                                                           Cl Cl                                                                              Cl     H Cl                                 HCO       CH.sub.3 CO   CH.sub.3                                                                           Cl H CF.sub.3                                                                             H Cl                                 HCO       C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     H H                                  HCO       C.sub.2 H.sub.5 CO                                                                          H    Cl H Cl     H Cl                                 HCO       C.sub.2 H.sub.5 CO                                                                          CH.sub.3 CO                                                                        Cl Cl                                                                              Cl     H Cl                                 HCO       CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H CF.sub.3                                                                             H Cl                                 HCO       C.sub.2 H.sub.5 OCO                                                                         H    Cl H CF.sub.3                                                                             H H                                  HCO       C.sub.2 H.sub.5 OCO                                                                         H    F  H CF.sub.3                                                                             H F                                  HCO                                                                                      ##STR31##    H    Cl Cl                                                                              Cl     H H                                  HCO       C.sub.6 H.sub.5 CO                                                                          H    Cl H Cl     H Cl                                 HCO       C.sub.6 H.sub.5 OCO                                                                         H    F  F F      F F                                  CH.sub.3CO                                                                              H             H    NO.sub.2                                                                         H NO.sub.2                                                                             H H                                  CH.sub.3CO                                                                              H             H    NO.sub.2                                                                         H CF.sub.3                                                                             H H                                  CH.sub.3CO                                                                              CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  CH.sub.3CO                                                                              CH.sub.3 CO   H    Cl H Cl     H Cl                                 CH.sub.3CO                                                                              CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H Cl     H H                                  CH.sub.3CO                                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H H                                  CH.sub.3CO                                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H Cl                                 CH.sub.3CO                                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     H H                                  CH.sub.3CO                                                                              CF.sub.3 CO   H    Cl H Cl     H Cl                                 CH.sub.3CO                                                                              CF.sub.3 CO   H    Cl H CF.sub.3                                                                             H H                                  CH.sub.3CO                                                                              ClCH.sub.2 CO H    Cl H OCF.sub.3                                                                            H Cl                                 CH.sub.3CO                                                                              CH.sub.3 OCH.sub.2 CO                                                                       H    Cl H OCF.sub.3                                                                            H Cl                                 CH.sub.3CO                                                                              CH.sub.3 SCH.sub.2 CO                                                                       H    Cl H SCF.sub.3                                                                            H Cl                                 CH.sub.3CO                                                                              Cl.sub.2 CHCO H    F  H SCF.sub.3                                                                            H F                                  CH.sub.3CO                                                                              Cl.sub.2 CHCO H    F  H SO.sub.2 CF.sub.3                                                                    H F                                  CH.sub.3CO                                                                               ##STR32##    H    F  H SO.sub.2 CF.sub.3                                                                    H F                                  CH.sub.3CO                                                                              BrCH.sub.2 CO H    F  F F      F F                                  HONCH     H             H    Cl H Cl     H H                                  HONCH     H             H    Cl H CF.sub.3                                                                             H H                                  HONCH     H             H    Cl Cl                                                                              Cl     H H                                  HONCH     H             H    F  F F      F F                                  HONCH     CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  HONCH     CH.sub.3 CO   H    Cl H Cl     H Cl                                 HONCH     C.sub.2 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H Cl                                 HONCH     C.sub.2 H.sub.5 CO                                                                          H    Cl H Cl     H H                                  HONCH     C.sub.2 H.sub.5 CO                                                                          C.sub.2 H.sub.5 CO                                                                 Cl H OCF.sub.3                                                                            H Cl                                 HONCH     CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H OCF.sub.3                                                                            H Cl                                 HONCH     CF.sub.3 CO   CF.sub.3 CO                                                                        Cl H SCF.sub.3                                                                            H Cl                                 HONCH     CF.sub.3 CO   H    Cl H OCH.sub.3                                                                            H Cl                                 HONCH     ClCH.sub.2 CO H    Cl H SCH.sub.3                                                                            H Cl                                 HONCH     Cl.sub.2 CHCO H    Cl H SO.sub.2 CH.sub.3                                                                    H Cl                                 HONCH     CH.sub.3 OCH.sub.2 CO                                                                       H    Cl H SO.sub.2 CH.sub.3                                                                    H Cl                                 HONCH     CH.sub.3 OCH.sub.2 CO                                                                       H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 HONCH     CH.sub.3 SCH.sub.2 CO                                                                       H    Cl Cl                                                                              Cl     H H                                  CH.sub.3 ONCH                                                                           H             H    CF.sub.3                                                                         H CF.sub.3                                                                             H H                                  CH.sub.3 ONCH                                                                           H             H    F  H F      H F                                  CH.sub.3 ONCH                                                                           H             H    F  H F      H F                                  CH.sub.3 OCHN                                                                           CH.sub.3 CO   H    F  F F      F F                                  CH.sub.3 ONCH                                                                           CH.sub.3 CO   H    Cl H Cl     H Cl                                 CH.sub.3 ONCH                                                                           CH.sub.3 CO   H    Cl H Cl     H H                                  CH.sub.3 ONCH                                                                           C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     H H                                  CH.sub.3 ONCH                                                                           C.sub.2 H.sub.5 O                                                                           H    CF.sub.3                                                                         H CF.sub.3                                                                             H H                                  CH.sub.3 ONCH                                                                           C.sub.2 H.sub.5 CO                                                                          H    CF.sub.3                                                                         H CF.sub.3                                                                             H CF.sub.3                           CH.sub.3 ONCH                                                                           CF.sub.3 CO   H    Cl H CF.sub.3                                                                             H H                                  CH.sub.3 ONCH                                                                           C.sub.6 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H Cl                                 CH.sub.3 ONCH                                                                           ClCH.sub.2 CO H    Cl H OCF.sub.3                                                                            H Cl                                 CH.sub.3 ONCH                                                                           ICH.sub.2 CO  H    Cl Cl                                                                              Cl     H H                                  CH.sub.3 ONCH                                                                           BrCH.sub.2 CO H    F  F F      F F                                  CH.sub.3 ONCH                                                                           C.sub.2 H.sub.5 OCO                                                                         H    Cl H OCF.sub.3                                                                            H H                                  CH.sub. 3 ONCH                                                                          CH.sub.3 CO   CH.sub.3                                                                           Cl H SCF.sub.3                                                                            H Cl                                 CH.sub.3 ONCH                                                                           CH.sub.3 CO   H    Cl H CF.sub.3                                                                             H Cl                                 CH.sub.3 ONCH                                                                           C.sub.2 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H Cl                                 H.sub.2 NSO.sub.2                                                                       H             H    CF.sub.3                                                                         H CF.sub.3                                                                             H H                                  H.sub.2 NSO.sub.2                                                                       H             H    Cl H Cl     H Cl                                 H.sub.2 NSO.sub.2                                                                       H             H    Cl H Cl     H H                                  H.sub.3 NSO.sub.2                                                                       CH.sub.3 CO   H    Cl Cl                                                                              Cl     H Cl                                 H.sub.2 NSO.sub.2                                                                       CH.sub.3 CO   H    F  F F      F F                                  H.sub.2 NSO.sub.2                                                                       CH.sub.3 CO   H    F  F CF.sub.3                                                                             F F                                  H.sub.2 NSO.sub.2                                                                       C.sub.2 H.sub.5 CO                                                                          H    F  F OCF.sub.3                                                                            F F                                  H.sub.2 NSO.sub.2                                                                       C.sub.2 H.sub.5 CO                                                                          H    F  F SCF.sub.3                                                                            F F                                  H.sub.2 NSO.sub.2                                                                       C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.3                                                                            H Cl                                 H.sub.2 NSO.sub.2                                                                       CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H SCF.sub.3                                                                            H Cl                                 H.sub. 2 NSO.sub.2                                                                      CH.sub.3 CO   CH.sub.3                                                                           Cl H SOCF.sub.3                                                                           H Cl                                 H.sub.2 NSO.sub.2                                                                       ClCH.sub.2 CO H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 H.sub.2 NSO.sub.2                                                                       BrCH.sub.2 CO H    Cl H SO.sub.2 CH.sub.3                                                                    H H                                  H.sub.2 NSO.sub.2                                                                       ICH.sub.2 CO  H    Cl H SO.sub.2 CF.sub.3                                                                    H H                                  H.sub.2 NSO.sub.2                                                                       C.sub.6 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H Cl                                 H.sub.2 NSO.sub.2                                                                       C.sub.2 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H H                                  H.sub.2 NSO.sub.2                                                                       CF.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  H         C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.3                                                                            H Cl                                 H         CH.sub.3 CO   H    Cl H OCF.sub.3                                                                            H Cl                                 H                                                                                        ##STR33##    H    Cl H OCF.sub.3                                                                            H Cl                                 H         n-C.sub.3 H.sub.7 CO                                                                        H    Cl H OCF.sub.3                                                                            H Cl                                 H         CH.sub.3 OCO  H    Cl H OCF.sub.3                                                                            H Cl                                 H         CH.sub.3 OCO  H    Cl H SO.sub.2 CH.sub.3                                                                    H Cl                                 H         CH.sub.3 CO   H    Cl H SO.sub.2 CH.sub.3                                                                    H Cl                                 H         C.sub.2 H.sub.5 CO                                                                          H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 H                                                                                        ##STR34##    H    Cl H SO.sub.2 CH.sub.3                                                                    H Cl                                 H         n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 H         n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 H         CH.sub.3 CO   H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 H         C.sub.2 H.sub.5 CO                                                                          H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 H         CH.sub.3 CO   H    Br H OCF.sub.3                                                                            H Br                                 H         C.sub.2 H.sub.5 CO                                                                          H    Br H OCF.sub.3                                                                            H H                                  H         n-C.sub.3 H.sub.7 CO                                                                        H    Br H OCF.sub.3                                                                            H H                                  H                                                                                        ##STR35##    H    Br H OCF.sub.3                                                                            H H                                  H         CH.sub.3 OCO  H    Br H OCF.sub.3                                                                            H H                                  H         CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H Br                                 H         CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H H                                  H         C.sub.2 H.sub.5 CO                                                                          H    Br H SCF.sub.3                                                                            H H                                  H         n-C.sub.3 H.sub.7 CO                                                                        H    Br H SCF.sub.3                                                                            H H                                  H         C.sub.2 H.sub.5 CO                                                                          H    Cl H H      H Cl                                 H         C.sub.2 H.sub.5 CO                                                                          H    Br H Br     H Br                                 H         C.sub.2 H.sub.5 CO                                                                          H    Cl H Cl     H H                                  H         C.sub.2 H.sub.5 CO                                                                          H    Br H Br     H H                                  NO        C.sub.2 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H Cl                                 NO        CH.sub.3 CO   H    Cl H CF.sub.3                                                                             H Cl                                 NO                                                                                       ##STR36##    H    Cl H CF.sub.3                                                                             H Cl                                 NO        CH.sub.3 OCO  H    Cl H CF.sub.3                                                                             H Cl                                 NO        n-C.sub.3 H.sub.7 CO                                                                        H    Cl H CF.sub.3                                                                             H Cl                                 NO        CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H CF.sub.3                                                                             H Cl                                 NO        C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.3                                                                            H H                                  NO                                                                                       ##STR37##    H    Cl H OCF.sub.3                                                                            H H                                  NO        n-C.sub.4 H.sub.9 CO                                                                        H    Cl H OCF.sub.3                                                                            H H                                  NO        C.sub.2 H.sub.5 CO                                                                          H    Cl H SCF.sub.3                                                                            H Cl                                 NO        n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SCF.sub.3                                                                            H Cl                                 NO                                                                                       ##STR38##    H    Cl H SCF.sub.3                                                                            H Cl                                 NO        CH.sub.3 CO   H    Cl H SCF.sub.3                                                                            H Cl                                 NO        CH.sub.3 OCO  H    Cl H SCF.sub.3                                                                            H Cl                                 NO        CH.sub.3 OCO  H    Cl H OCF.sub.3                                                                            H H                                  NO        C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     H Cl                                 NO        CH.sub.3 CO   H    Cl Cl                                                                              Cl     H Cl                                 NO        CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  NO                                                                                       ##STR39##    H    Cl Cl                                                                              Cl     H Cl                                 NO        CH.sub.3 OCO  H    Cl Cl                                                                              Cl     H Cl                                 NO        CH.sub.3 CO   H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 NO        C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 NO        n-C.sub.3 H.sub.7 CO                                                                        H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 NO                                                                                       ##STR40##    H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 NO        CH.sub.3 OCO  H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 NO        C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.3                                                                            H Cl                                 NO        CH.sub.3 CO   H    Cl H OCF.sub.3                                                                            H Cl                                 NO                                                                                       ##STR41##    H    Cl H OCF.sub.3                                                                            H Cl                                 NO        n-C.sub.3 H.sub.7 CO                                                                        H    Cl H OCF.sub.3                                                                            H Cl                                 NO        CH.sub.3 OCO  H    Cl H OCF.sub.3                                                                            H Cl                                 NO        CH.sub.3 OCO  H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO        CH.sub.3 CO   H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO        C.sub.2 H.sub.5 CO                                                                          H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO                                                                                       ##STR42##    H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO        n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO        n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 NO        CH.sub.3 CO   H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 NO        C.sub.2 H.sub. 5 CO                                                                         H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 NO        CH.sub.3 CO   H    Br H OCF.sub.3                                                                            H Br                                 NO        C.sub.2 H.sub.5 CO                                                                          H    Br H OCF.sub.3                                                                            H H                                  NO        n-C.sub.3 H.sub.7 CO                                                                        H    Br H OCF.sub.3                                                                            H H                                  NO                                                                                       ##STR43##    H    Br H OCF.sub.3                                                                            H H                                  NO        CH.sub.3 OCO  H    Br H OCF.sub.3                                                                            H H                                  NO        CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H Br                                 NO        CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H Br                                 NO        C.sub.2 H.sub.5 CO                                                                          H    Br H SCF.sub.3                                                                            H H                                  NO        n-C.sub.3 H.sub.7 CO                                                                        H    Br H SCF.sub.3                                                                            H H                                  NO        C.sub.2 H.sub.5 CO                                                                          H    Cl H H      H Cl                                 NO        C.sub.2 H.sub.5 CO                                                                          H    Br H Br     H Br                                 NO        C.sub.2 H.sub.5 CO                                                                          H    Cl H Cl     H H                                  NO        C.sub.2 H.sub.5 CO                                                                          H    Br H Br     H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.3                                                                            H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl H OCF.sub. 3                                                                           H Cl                                 NO.sub.2                                                                                 ##STR44##    H    Cl H OCF.sub.3                                                                            H Cl                                 NO.sub.2  n-C.sub.3 H.sub.7 CO                                                                        H    Cl H OCF.sub.3                                                                            H Cl                                 NO.sub.2  CH.sub.3 OCO  H    Cl H OCF.sub.3                                                                            H Cl                                 NO.sub.2  CH.sub.3 OCO  H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO.sub.2                                                                                 ##STR45##    H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO.sub.2  n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO.sub.2  n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 NO.sub.2  CH.sub.3 CO   H    Br H OCF.sub.3                                                                            H Br                                 NO.sub.2  C.sub.2 H.sub. 5 CO                                                                         H    Br H OCF.sub.3                                                                            H H                                  NO.sub.2  n-C.sub.3 H.sub.7 CO                                                                        H    Br H OCF.sub.3                                                                            H H                                  NO.sub.2                                                                                 ##STR46##    H    Br H OCF.sub.3                                                                            H H                                  NO.sub.2  CH.sub.3 OCO  H    Br H OCF.sub.3                                                                            H H                                  NO.sub.2  CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H Br                                 NO.sub.2  CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Br H SCF.sub.3                                                                            H H                                  NO.sub.2  n-C.sub.3 H.sub.7 CO                                                                        H    Br H SCF.sub.3                                                                            H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H H      H Cl                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Br H Br     H Br                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H Cl     H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Br H Br     H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl H CF.sub.3                                                                             H Cl                                 NO.sub.2                                                                                 ##STR47##    H    Cl H CF.sub.3                                                                             H Cl                                 NO.sub.2  CH.sub.3 OCO  H    Cl H CF.sub.3                                                                             H Cl                                 NO.sub.2  n-C.sub.3 H.sub.7 CO                                                                        H    Cl H CF.sub.3                                                                             H Cl                                 NO.sub.2  CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H CF.sub.3                                                                             H Cl                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.3                                                                            H H                                  NO.sub.2                                                                                 ##STR48##    H    Cl H OCF.sub.3                                                                            H H                                  NO.sub.2  n-C.sub.4 H.sub.9 CO                                                                        H    Cl H OCF.sub.3                                                                            H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H SCF.sub.3                                                                            H Cl                                 NO.sub.2  n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SCF.sub.3                                                                            H Cl                                 NO.sub.2                                                                                 ##STR49##    H    Cl H SCF.sub.3                                                                            H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl H SCF.sub.3                                                                            H Cl                                 NO.sub.2  CH.sub.3 OCO  H    Cl H SCF.sub.3                                                                            H Cl                                 NO.sub.2  CH.sub.3 OCO  H    Cl H OCF.sub.3                                                                            H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl Cl                                                                              Cl     H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  NO.sub.2                                                                                 ##STR50##    H    Cl Cl                                                                              Cl     H Cl                                 NO.sub.2  CH.sub.3 OCO  H    Cl Cl                                                                              Cl     H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 NO.sub.2  n-C.sub.3 H.sub.7 CO                                                                        H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 NO.sub.2                                                                                 ##STR51##    H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 NO.sub.2  CH.sub.3 OCO  H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   H    Cl H CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                               ##STR52##    H    Cl H CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub. 3 CO  H    Cl H CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              n-C.sub.3 H.sub.7 CO                                                                        H    Cl H CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.3                                                                            H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                               ##STR53##    H    Cl H OCF.sub.3                                                                            H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                              n-C.sub.4 H.sub.9 CO                                                                        H    Cl H OCF.sub.3                                                                            H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl H SCF.sub.3                                                                            H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SCF.sub.3                                                                            H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                               ##STR54##    H    Cl H SCF.sub.3                                                                            H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   H    Cl H SCF.sub.3                                                                            H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 OCO  H    Cl H SCF.sub. 3                                                                           H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 OCO  H    Cl H OCF.sub.3                                                                            H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                               ##STR55##    H    Cl Cl                                                                              Cl     H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   H    Cl Cl                                                                              Cl     H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.3 H.sub.7 CO                                                                          H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                               ##STR56##    H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.3                                                                            H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   Cl   Cl H OCF.sub.3                                                                            H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                               ##STR57##    H    Cl H OCF.sub.3                                                                            H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              n-C.sub.3 H.sub.7 CO                                                                        H    Cl H OCF.sub.3                                                                            H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 OCO  H    Cl H OCF.sub.3                                                                            H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 OCO  H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                               ##STR58##    H    Cl H SO.sub.3 CF.sub.3                                                                    H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SO.sub. 2 CF.sub.3                                                                   H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   H    Br H OCF.sub.3                                                                            H Br                                 PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 O                                                                           H    Br H OCF.sub.3                                                                            H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                              n-C.sub.3 H.sub.7 CO                                                                        H    Br H OCF.sub.3                                                                            H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                               ##STR59##    H    Br H OCF.sub.3                                                                            H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 OCO  H    Br H OCF.sub.3                                                                            H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H Br                                 PO(OC.sub.2 H.sub.5).sub.2                                                              CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Br H SCF.sub.3                                                                            H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                              n-C.sub.3 H.sub.7 CO                                                                        H    Br H SCF.sub.3                                                                            H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl H H      H Cl                                 PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 O                                                                           H    Br H Br     H Br                                 PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Cl H Cl     H H                                  PO(OC.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5 CO                                                                          H    Br H Br     H H                                  Cl        C.sub.2 H.sub.5 CO                                                                          H    Cl H CF.sub.3                                                                             H Cl                                 Cl        CH.sub.3 CO   H    Cl H CF.sub.3                                                                             H Cl                                 Cl                                                                                       ##STR60##    H    Cl H CF.sub.3                                                                             H Cl                                 Cl        CH.sub.3 OCO  H    Cl H CF.sub.3                                                                             H Cl                                 Cl        n-C.sub.3 H.sub.7 CO                                                                        H    Cl H CF.sub.3                                                                             H Cl                                 Cl        CH.sub.3 CO   CH.sub.3 CO                                                                        Cl H CF.sub.3                                                                             H Cl                                 Cl        C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.3                                                                            H H                                  Cl                                                                                       ##STR61##    H    Cl H OCF.sub.3                                                                            H H                                  Cl        n-C.sub.4 H.sub.9 CO                                                                        H    Cl H OCF.sub.3                                                                            H H                                  Cl        C.sub.2 H.sub.5 CO                                                                          H    Cl H SCF.sub.3                                                                            H Cl                                 Cl        n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SCF.sub.3                                                                            H Cl                                 Cl                                                                                       ##STR62##    H    Cl H SCF.sub.3                                                                            H Cl                                 Cl        CH.sub.3 CO   H    Cl H SCF.sub.3                                                                            H Cl                                 Cl        CH.sub.3 OCO  H    Cl H SCF.sub.3                                                                            H Cl                                 Cl        CH.sub.3 OCO  H    Cl H OCF.sub.3                                                                            H H                                  Cl        C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              Cl     H Cl                                 Cl        CH.sub.3 CO   H    Cl Cl                                                                              Cl     H Cl                                 Cl        CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  Cl                                                                                       ##STR63##    H    Cl Cl                                                                              Cl     H Cl                                 Cl        CH.sub.3 OCO  H    Cl Cl                                                                              Cl     H Cl                                 Cl        CH.sub.3 CO   H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 Cl        C.sub.2 H.sub.5 CO                                                                          H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 Cl        n-C.sub.3 H.sub.7 CO                                                                        H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 Cl                                                                                       ##STR64##    H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 Cl        CH.sub.3 OCO  H    Cl Cl                                                                              CF.sub.3                                                                             H Cl                                 Cl        C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.3                                                                            H Cl                                 Cl        CH.sub.3 CO   H    Cl H OCF.sub.3                                                                            H Cl                                 Cl                                                                                       ##STR65##    H    Cl H OCF.sub.3                                                                            H Cl                                 Cl        n-C.sub.3 H.sub.7 CO                                                                        H    Cl H OCF.sub.3                                                                            H Cl                                 Cl        CH.sub.3 OCO  H    Cl H OCF.sub.3                                                                            H Cl                                 Cl        CH.sub.3 OCO  H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 Cl        CH.sub.3 CO   H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 Cl        C.sub.2 H.sub.5 CO                                                                          H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 Cl                                                                                       ##STR66##    H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 Cl        n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 Cl        n-C.sub.3 H.sub.7 CO                                                                        H    Cl H SO.sub. 2 CClF.sub.2                                                                 H Cl                                 Cl        CH.sub.3 CO   H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 Cl        C.sub.2 H.sub.5 CO                                                                          H    Cl H SO.sub.2 CClF.sub.2                                                                  H Cl                                 Cl        CH.sub.3 CO   H    Br H OCF.sub.3                                                                            H Br                                 Cl        C.sub.2 H.sub.5 CO                                                                          H    Br H OCF.sub.3                                                                            H H                                  Cl        n-C.sub.3 H.sub.7 CO                                                                        H    Br H OCF.sub.3                                                                            H H                                  Cl                                                                                       ##STR67##    H    Br H OCF.sub.3                                                                            H H                                  Cl        CH.sub.3 OCO  H    Br H OCF.sub.3                                                                            H H                                  Cl        CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H Br                                 Cl        CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H H                                  Cl        C.sub.2 H.sub.5 CO                                                                          H    Br H SCF.sub.3                                                                            H H                                  Cl        n-C.sub.3 H.sub.7 CO                                                                        H    Br H SCF.sub.3                                                                            H H                                  Cl        C.sub.2 H.sub.5 CO                                                                          H    Cl H H      H Cl                                 Cl        C.sub.2 H.sub.5 CO                                                                          H    Br H Br     H Br                                 Cl        C.sub.2 H.sub.5 CO                                                                          H    Cl H Cl     H H                                  Cl        C.sub.2 H.sub.5 CO                                                                          H    Br H Br     H H                                  H         HCO           H    Cl H Cl     H Cl                                 H         HCO           H    Cl Cl                                                                              Cl     H H                                  H         HCO           H    Cl H OCF.sub.3                                                                            H Cl                                 H         HCO           H    Cl H SCF.sub.3                                                                            H Cl                                 H         HCO           H    Cl H OCF.sub.3                                                                            H H                                  H         HCO           H    Cl H CF.sub.3                                                                             H Cl                                 H         HCO           H    Br H Br     H Br                                 H         HCO           H    Cl H Br     H Cl                                 H         HCO           H    Cl H SO.sub.2 CF.sub.3                                                                    H H                                  H         HCO           H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO.sub.2  HCO           H    Cl H Cl     H Cl                                 NO.sub.2  HCO           H    Cl Cl                                                                              Cl     H H                                  NO.sub.2  HCO           H    Cl H OCF.sub.3                                                                            H Cl                                 NO.sub.2  HCO           H    Cl H OCF.sub.3                                                                            H H                                  NO.sub.2  HCO           H    Cl H SCF.sub.3                                                                            H Cl                                 NO.sub.2  HCO           H    Cl H SCF.sub.3                                                                            H H                                  NO.sub.2  HCO           H    Cl H SO.sub.2 CF.sub.3                                                                    H H                                  NO.sub.2  HCO           H    Cl H SO.sub.2 CF.sub.3                                                                    H Cl                                 NO.sub.2  HCO           H    Br H Br     H Br                                 NO.sub.2  HCO           H    Cl H Br     H Cl                                 NO.sub.2  HCO           H    Cl H Br     H Br                                 NO.sub.2  HCO           H    Br H OCF.sub.3                                                                            H Br                                 NO.sub.2  HCO           H    Br H OCF.sub.3                                                                            H H                                  NO.sub.2  HCO           H    Br H SCF.sub.3                                                                            H Br                                 NO.sub.2  HCO           H    I  H OCF.sub.3                                                                            H H                                  NO.sub.2  CH.sub.3 CO   H    Cl H Cl     H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl Cl                                                                              Cl     H H                                  NO.sub.2  CH.sub.3 CO   H    Cl H OCF.sub.3                                                                            H Cl                                 NO.sub.2  CH.sub.3 CO   H    Br H Br     H Br                                 NO.sub.2  CH.sub.3 CO   H    Cl H Br     H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl H Br     H Br                                 NO.sub.2  CH.sub.3 CO   H    Br H Cl     H Cl                                 NO.sub.2  CH.sub.3 CO   H    Br H OCF.sub.3                                                                            H H                                  NO.sub.2  CH.sub.3 CO   H    Br H OCF.sub.3                                                                            H Br                                 NO.sub.2  CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H H                                  NO.sub.2  CH.sub.3 CO   H    Br H SCF.sub.3                                                                            H Br                                 NO.sub.2  CH.sub.3 CO   H    Br H SO.sub.2 CH.sub.3                                                                    H H                                  NO.sub.2  CH.sub.3 CO   H    Br H SO.sub.2 CF.sub.3                                                                    H Br                                 NO.sub.2  CH.sub.3 CO   H    Br H SO.sub.2 CF.sub.3 Cl                                                                 H H                                  NO.sub.2  CH.sub.3 CO   H    Br H SO.sub.2 CF.sub.2 Cl                                                                 H Br                                 NO.sub.2  CH.sub.3 CO   H    Cl H OCF.sub.2 Cl                                                                         H H                                  NO.sub.2  CH.sub.3 CO   H    Cl H OCF.sub.2 CHF.sub.2                                                                  H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl H OCHF.sub.2                                                                           H H                                  NO.sub.2  CH.sub.3 CO   H    Cl H OCHF.sub.2                                                                           H Cl                                 NO.sub.2  CH.sub.3 CO   H    Cl H OCH.sub.2 CF.sub.3                                                                   H H                                  NO.sub.2  CH.sub.3 CO   H    Cl H OCH.sub.2 CF.sub.3                                                                   H Cl                                 NO.sub.2  CH.sub.3 CO   H    Br H OCH.sub.2 CF.sub.3                                                                   H H                                  NO.sub.2  CH.sub.3 CO   H    Br H OCH.sub.2 CF.sub.3                                                                   H Br                                 NO.sub.2  CH.sub.3 CO   H    Br H CF.sub.3                                                                             H H                                  NO.sub.2  CH.sub.3 CO   H    Br H CF.sub.3                                                                             H Br                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H OCHF.sub.2                                                                           H Cl                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H OCHF.sub.2                                                                           H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.2 CHF.sub.2                                                                  H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.2 CHF.sub.2                                                                  H Cl                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H CHF.sub.2                                                                            H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H CHF.sub.2                                                                            H Cl                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.2 CHFCl                                                                      H H                                  NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H OCF.sub.2 CHFCl                                                                      H Cl                                 NO.sub.2  C.sub.2 H.sub.5 CO                                                                          H    Cl H Br     H Cl                                 __________________________________________________________________________

Some of the substituted 5-amino-1-phenylpyrazoles of the formula (I)which are to be used according to the invention are known (see: J. Org.Chem. 36, 2972-2974 [1971]; J. Heterocycl. Chem. 7, 345-349 [1970] andC.A. 62: 13137 c).

Substituted 5-amino-1-phenyl-pyrazoles which were hitherto unknown arethose of the formula (I') ##STR68## in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷and R⁸ have the meaning given above, except that, when R¹ representshydrogen, methyl or optionally substituted phenyl, R⁴ and R⁶ cannotsimultaneously represent the nitro group.

The hitherto unknown substituted 5-amino-1-phenyl-pyrazoles of theformula (I') are obtained if

a) phenylhydrazines of the formula (II) ##STR69## in which R⁴, R⁵, R⁶,R⁷ and R⁸ have the meaning given above,

are reacted with acrylonitrile derivatives of the formula (III)##STR70## in which R¹ has the meaning given above and

A represents halogen, hydroxyl or alkoxy, or, in the case in which R¹represents hydrogen, also with 2-halogenoacrylonitriles of the formula(IIIa) ##STR71## in which Hal represents halogen, in particular chlorineor bromine,

or with 2,3-dihalogenopropionitriles of the formula (IIIb) ##STR72## inwhich Hal' represents halogen, in particular chlorine or bromine,

the reaction either being carried out to give the phenylhydrazinederivatives of the formula (IV) ##STR73## in which R⁴, R⁵, R⁶, R⁷ and R⁸have the meaning given under formula (I') and

Z represents one of the radicals ##STR74## wherein Hal and Hal'represent identical or different halogen atoms, in a first stage, ifappropriate in the presence of a diluent and if appropriate in thepresence of a reaction auxiliary, the product being subjected to acyclization reaction in a second stage, if appropriate in the presenceof a diluent and, if appropriate, in the presence of an acid-bindingagent, or cyclization being carried out directly in one reaction stepwithout isolation of the intermediate of the formula (IV), ifappropriate in the presence of a diluent, to give the 5-amino-pyrazolesof the formula (Ia) ##STR75## in which R¹, R⁴, R⁵, R⁶, R⁷ and R⁸ havethe meaning given above,

or if

(b) the 5-amino-pyrazoles of the formula (Ia) ##STR76## in which R¹, R⁴,R⁵, R⁶, R⁷ and R⁸ have the above meaning,

which are obtainable by process (a) are reacted in a generally customarymanner with acylating agents or alkylating agents of the formula (V)

    R.sup.14 --A'                                              (V)

in which

R¹⁴ represents alkyl or a radical ##STR77## wherein X and R¹² have theabove meaning, and

A' represents an electron-attracting leaving group, or withiso(thio)cyanates of the formula (VI)

    R.sup.15 --N═C═X                                   (VI)

in which

R¹⁵ represents alkyl or optionally substituted aryl and

X has the above meaning,

if appropriate in the presence of a diluent, and if appropriate in thepresence of an acid-binding agent, to give the 5-amino-pyrazolesalkylated or acylated at the nitrogen, of the formula (Ib) ##STR78## inwhich R¹, R², R⁴, R⁵, R⁶, R⁷ and R⁸ have the above meaning and

R^(3') represents the same radicals as R³ given above, with theexception of the hydrogen radical,

or if

(c) the 5-amino-pyrazoles of the formula (Ic) ##STR79## in which R², R³,R⁴, R⁵, R⁶, R⁷ and R⁸ have the above meaning,

which are unsubstituted in the 4-position and are obtainable by process(a) or (b), are substituted in the 4-position, likewise in a generallycustomary manner, using electrophilic agents of the formula (VII)

    R.sup.1' --E                                               (VII)

in which

R^(1') represents halogen, nitroso, nitro, alkyl, formyl, alkanoyl,aroyl, hydroxysulphonyl or chlorosulphonyl and

E represents an electron-attracting leaving grouping,

or using other customary electrophilic reagents, if appropriate in thepresence of a diluent and, if appropriate, in the presence of a catalystor a reaction auxiliary, or if

(d) the 4-chlorosulphonyl-5-amino-pyrazoles obtainable by process (c) ofthe formula (Id) ##STR80## in which R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ havethe above meaning, are substituted at the chlorosulphonyl group in the4-position, using amines of the formula (VIII) ##STR81## in which R¹⁶and R¹⁷ independently of one another represent hydrogen or alkyl,

or using an alkali metal fluoride of the formula (IX)

    Me.sup.⊕ F.sup.⊖                               (IX)

in which

Me.sup.⊕ represents an alkali metal cation, if appropriate in thepresence of a diluent and, if appropriate, in the presence of anacid-binding agent, or if

(e) the 4-acyl-5-amino-pyrazoles of the formula (Ie) ##STR82## in whichR², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R¹⁰ have the above meaning,

which are obtainable by the process (c) or (f), are reacted withhydroxylamine derivatives of the formula (X)

    H.sub.2 N--OR.sup.11                                       (X)

in which

R¹¹ has the meaning given above, or with their hydrogen halide additionsalts such as hydrochlorides (HCL salts), if appropriate in the presenceof a diluent and, if appropriate, in the presence of an acid-bindingagent, or if

(f) 4-cyano-5-amino-pyrazoles of the formula (XI) ##STR83## in which R²,R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the meaning given above,

are reacted with formic acid and Raney nickel to give the corresponding5-amino-4-formyl-pyrazoles of the formula (If) ##STR84## in which R²,R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the meaning given above.

If, for example, 2-chloroacrylonitrile and2,6-dichloro-4-trifluoromethyl-phenylhydrazine are used as startingmaterials, the course of the reaction of preparation process (a) can berepresented by the following equation: ##STR85##

If, for example, 5-amino-1-(2,4,6-trichlorophenyl)-pyrazole andpropionyl chloride are used as starting materials, the course of thereaction of preparation process (b) can be represented by the followingequation: ##STR86##

If, for example, 5-propionamido-1-(2,3,4-trichlorophenyl)-pyrazole andnitric acid are used as starting materials, the course of the reactionof preparation process (c) can be represented by the following equation:##STR87##

If, for example,5-acetamido-4-chlorosulphonyl-1-(2,4,6-trichlorophenyl)-pyrazole anddiethylamine are used as starting materials, the course of the reactionof preparation process (d) can be represented by the following equation:##STR88##

If, for example, 5-acetamido-4-acetyl-1-(pentafluorophenyl)-pyrazole and0-methyl-hydroxylamine hydrochloride are used as starting materials, thecourse of the reaction of preparation process (e) can be represented bythe following equation: ##STR89##

If, for example, 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)-pyrazole andformic acid are used as starting material, and Raney nickel is used as areducing agent, the course of the reaction of process (f) according tothe invention can be represented by the following equation: ##STR90##

Formula (II) gives a general definition of the phenylhydrazines requiredas starting materials for carrying out preparation process (a) accordingto the invention. In this formula (II), R⁴, R⁵, R⁶, R⁷ and R⁸ preferablyrepresent those substituents which have already been mentioned in thedescription of the substances which can be used according to theinvention, of the formula (I), as being preferred for these radicals.

The majority of the phenylhydrazines of the formula (II) are known orcan be prepared by known processes in a simple, analogous manner (see:for example, HoubenWeyl "Methoden der organischen Chemie" (Methods oforganic chemistry), Volume X,2, page 203, Thieme Verlag Stuttgart 1967)by, for example, reacting the known anilines of the formula (XII)##STR91## in which R⁴, R⁵, R⁶, R⁷ and R⁸ have the meaning given above,

with sodium nitrite, in the presence of an acid, such as, for example,sulphuric acid, and then with tin(II) chloride, likewise in the presenceof an acid, such as, for example, hydrochloric acid, at temperaturesbetween -20° C. and +80° C.

Formula (III) gives a general definition of the acrylonitrilederivatives furthermore required as starting materials for carrying outpreparation process (a). In this formula (III), R¹ preferably representsthose radicals which have already been mentioned in the description ofthe substances which can be used according to the invention, of theformula (I), as being preferred for these substituents. A preferablyrepresents chlorine or bromine, hydroxyl, methoxy or ethoxy. Theacrylonitrile derivatives of the formula (III) are known (see: forexample, DE-OS (German Published Specification) 3,129,429, EuropeanPatent 34,945; J. Chem. Soc. D 1970, 1255; Can. J. Chem. 48, 2104-2109(1970); J. Heterocyclic Chem. 19, 1267-1273 (1982); and Can. J. Chem.51, 1239-1244 [1973]), or can be obtained by processes known from theliterature in a simple analogous manner. The 2-halogeno-acrylonitrilesof the formula (IIIa) and the 2,3-dihalogeno-propionitriles of theformula (IIIb) are likewise known (see, for example, J. Prakt. Chemie321, 93 [1979]; J. Heterocyclic Chem. 19, 1265 [1982]; and J.Heterocyclic Chem. 19, 1267 [1982]).

Formula (Ia) gives a general definition of the 5-amino-pyrazolesrequired as starting materials for carrying out preparation process (b).In this formula (Ia), R¹, R⁴, R⁵, R⁶, R⁷ and R⁸ preferably representthose radicals which have already been mentioned in the description ofthe substances which can be used according to the invention, of theformula (I), as being preferred for these radicals.

The 5-amino-pyrazoles of the formula (Ia) were hitherto unknown. Theyare obtained by preparation process (a).

Formula (V) gives a general definition of the alkylating and acylatingagents furthermore required as starting materials for carrying outpreparation process (b). In this formula (V), R¹⁴ preferably representsa straight-chain or branched alkyl having up to 4 carbon atoms, andfurthermore represents a radical --C wherein X and R¹² preferablyrepresent those radicals which have already been mentioned for theseradicals, in the description of the substances which can be usedaccording to the invention, of the formula (I). A' preferably representschlorine, bromine or iodine, p-toluenesulphonyloxy, alkoxysulphonyloxyor acyloxy. The alkylating and acylating agents of the formula (V) aregenerally known compounds of organic chemistry.

Formula (VI) gives a general definition of the iso(thio)cyanates whichcan alternatively be used as starting materials for carrying outpreparation process (b). In this formula, X preferably represents oxygenor sulphur, and R¹⁵ preferably represents straight-chain or branchedalkyl having up to 4 carbon atoms, or phenyl which is optionallymonosubstituted to trisubstituted by identical or differentsubstituents, suitable substituents being halogen, or alkyl, alkoxy orhalogenoalkyl, each of which is straight-chain or branched and each ofwhich has up to 4 carbon atoms and, in the case of halogenoalkyl, up to9 identical or different halogen atoms. R¹⁵ represents, in particular,methyl or ethyl, or phenyl which is optionally monosubstituted totrisubstituted by identical or different substituents from amongstfluorine, chlorine, methyl, methoxy and trifluoromethyl.

The iso(thio)cyanates of the formula (VI) are likewise generally knowncompounds of organic chemistry.

Formula (Ic) gives a general definition of the 5-amino-pyrazolesrequired as starting materials for carrying out preparation process (c).In this formula (Ic), R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ preferably representthose radicals which have already been mentioned in the description ofthe substances which can be used according to the invention, of theformula (I), as being preferred for these substituents. The5-amino-pyrazoles of the formula (Ic) were hitherto unknown. They areobtained by preparation process (a) or (b).

Formula (VII) gives a general definition of the electrophilic agentsfurthermore required as starting materials for carrying out preparationprocess (c). In this formula (VII), R^(1') preferably representschlorine, bromine, nitroso, nitro, hydroxysulphonyl or chlorosulphonyl,formyl, and straight-chain or branched alkyl or alkanoyl, each having upto 6 carbon atoms, or represents benzoyl which is optionallymonosubstituted or polysubstituted by identical or differentsubstituents, suitable substituents being halogen, in particularfluorine, chlorine or bromine, and alkyl, alkoxy or halogenoalkyl, eachof which is straight-chain or branched and each of which has up to 4carbon atoms and, in the case of halogenoalkyl, up to 9 identical ordifferent halogen atoms, in particular methyl, methoxy ortrifluoromethyl. E preferably represents halogen, in particular chlorineor bromine, hydroxyl, alkyl- or arylsulphonyloxy, alkanoyloxy oraroyloxy. Other electrophilic reagents which can be used are sulphurylchloride, phosphorus oxychloride/dimethylformamide, nitrating acid andother substances customarily used for electrophilic substitutions. Theelectrophilic agents of the formula (VII), like the other customaryelectrophilic reagents, are generally known compounds. Formula (Id)gives a general definition of the 4-chlorosulphonyl-5-amino-pyrazolesrequired as starting materials for carrying out preparation process (d).In this formula (Id), R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ preferably representthose radicals which have already been mentioned in the description ofthe substances which can be used according to the invention, of theformula (I), as being preferred for these substituents. The4-chlorosulphonyl-5-amino-pyrazoles were hitherto unknown. They areobtained by preparation process (c).

Formula (VIII) gives a general definition of the amines furthermorerequired as starting materials for carrying out preparation process (d).In this formula (VIII), R¹⁶ and R¹⁷ independently of one anotherpreferably represent hydrogen or straight-chain or branched alkyl havingup to 4 carbon atoms.

Formula (IX) gives a general definition of the alkali metal fluoridesalternatively required as starting materials for carrying outpreparation process (d). In this formula (IX), M⊕ preferably representsa sodium or potassium cation.

The amines of the formula (VIII), like the alkali metal fluorides of theformula (IX), are generally known compounds.

Formula (Ie) gives a general definition of the 4-acyl-5-amino-pyrazolesrequired as starting materials for carrying out preparation process (e).In this formula (Ie), R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R¹⁰ preferablyrepresent those radicals which have already been mentioned in thedescription of the substances which can be used according to theinvention of the formula (I) as being preferred for these substituents.The 4-acyl-5-amino-pyrazoles of the formula (Ie) were hitherto unknown.They are obtained by preparation process (c) or (f).

Formula (X) gives a general definition of the hydroxylamine derivativesfurthermore required as starting materials for carrying out preparationprocess (e). In this formula (X), R¹¹ preferably represents thoseradicals which have already been mentioned in the description of thesubstances which can be used according to the invention, of the formula(I), as being preferred for these substituents. The hydroxylaminederivatives of the formula (X) and their hydrogen halide salts aregenerally known compounds.

Formula (XI) gives a general definition of the 4-cyano-5-amino-pyrazolesrequired as starting materials for carrying out preparation process (f).In this formula (XI), R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ preferably representthose radicals which have already been mentioned in the description ofthe substances which can be used according to the invention, of theformula (I), as being preferred for these substituents. Some of the4-cyano-5-amino-pyrazoles of the formula (XI) are known (see, forexample, European Patent 26,034; European Patent 34,945; European Patent53,687; DE-OS (German Published Specification) 3,226,496 and DE-OS(German Published Specification) 3,226,513) and some of them form thesubject of (German Patent Application 3,337,543 of Oct. 15, 1983). Theyare obtained for example, in a manner analogous to preparation process(a), if phenylhydrazines of the formula (II) ##STR92## in which R⁴, R⁵,R⁷ and R⁸ have the meaning given above, are reacted with the knownethoxymethylenemalodinitriles of the formula (XII) ##STR93## ifappropriate in the presence of a diluent, such as, for example, ethanol,and, if appropriate, in the presence of an acid-binding agent, such as,for example, sodium acetate, at temperatures of between -20° C. and+150° C.

Diluents which can be used for carrying out preparation process (a) andare suitable for both the first and the second reaction stage are inertorganic solvents. Alcohols, such as methanol, ethanol, propanol,butanol, ethylene glycol or ethylene glycol monomethyl or ethyl etherare preferably used.

Suitable reaction auxiliaries for carrying out the first stage ofpreparation process (a) are organic or inorganic acids. Sulphuric acidor acetic acid, if appropriate also in the presence of a buffersubstance, such as, for example, sodium acetate, are preferably used.

In carrying out the first stage of preparation process (a), the reactiontemperatures can be varied within certain ranges. In general, thereaction is carried out at between -30° and +50° C., preferably between-20° and +20° C.

Suitable acid-binding agents for carrying out the second stage ofpreparation process (a) are all inorganic and organic bases which cancustomarily be used. Alkali metal carbonates or bicarbonates, such assodium carbonate, potassium carbonate or potassium bicarbonate, arepreferably used.

In carrying out the second stage of preparation process (a), thereaction temperatures can, as in the single-stage reaction procedure, bevaried within a wide range. In general the reaction is carried out atbetween 0° C. and 200° C., preferably between 50° C. and +150° C.

In carrying out preparation process (a), in general 1.0 to 3.0 molspreferably 1.0 to 1.5 mols of the acrylonitrile derivative of theformula (III) or (IIIa) or of 2,3-dichloropropionitrile of the formula(IIIb) are employed per mol of phenylhydrazine of the formula (II), bothin the single-stage reaction procedure and in the two-stage reactionprocedure, and, in the case of the two-stage process, if appropriate 1.0to 10.0 mols of reaction auxiliary are employed in the first stage, and,if appropriate, 1.0 to 10.0 mols of acid-binding agent are employed inthe second stage.

Working-up and isolation of the reaction products are carried out bycustomary methods, for example by removing the organic diluent,precipitating the reaction product in water, and filtering off theresulting product under suction and drying it.

Suitable diluents for carrying out preparation process (b) are likewiseinert organic solvents. Preferably used compounds are aliphatic oraromatic, optionally halogenated hydrocarbons, such as, for example,benzine, benzene, toluene, xylene, pentane, hexane, heptane,cyclohexane, petroleum ether, ligroin, methylene chloride, chloroform,carbon tetrachloride, chlorobenzene or dichlorobenzene, ethers, such asdiethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethyleneglycol diethyl ether or ethylene glycol dimethyl ether, ketones, such asacetone, butanone, methyl isopropyl ketone or methyl isobutyl ketone,esters such as ethyl acetate, nitriles, such as acetonitrile orpropionitrile, amides, such as dimethylformamide, dimethylacetamide,N-methylpyrrolidone or hexamethylphosphoric acid triamide. If acylatingor alkylating agents of the formula (V) or (VI) are used in liquid form,it is also possible to employ these in an appropriate excess, as adiluent.

Suitable acid-binding agents for carrying out preparation process (b)are all inorganic and organic bases which can customarily be used.Preferably used compounds are alkali metal hydrides, hydroxides, amides,carbonates or bicarbonates, such as, for example, sodium hydride, sodiumamide, sodium hydroxide, sodium carbonate or sodium bicarbonate, ortertiary amines, such as, for example, triethylamine,N,N-dimethylaniline, pyridine, 4-(N,N-dimethylamino)-pyridine,diazabicyclooctane (DABCO), diazabicyclononene (DBN) ordiazabicycloundecene (DBU).

In carrying out preparation process (b), the reaction temperatures canbe varied within a wide range. In general, the reaction is carried outat between -20° C. and +150° C., preferably between 0° C. and +100° C.

In carrying out preparation process (b), in general 1.0 to 20.0 molspreferably 1.0 to 15.0 mols of acylating or alkylating agent of theformula (V) or (VI) and, if appropriate, -1.0 to 3.0 mols, preferably1.0 to 2.0 mols, of acid-binding agent are employed per mol of5-amino-pyrazole of the formula (Ia). The reaction procedure andworking-up and isolation of the reaction products of the formula (Ib)are carried out in a generally customary manner.

Suitable diluents for carrying out preparation process (c) are allsolvents which can customarily be used for such electrophilicsubstitutions. Preferably, the acids or mixtures which constitutesuitable reagents, such as, for example, sulphuric acid, chlorosulphonicacid, nitric acid, nitrating acid, sulfuryl chloride, phosphorusoxychloride/dimethylformamide or nitrating acid, are simultaneously usedas diluents. Inert organic solvents, such as, for example, glacialacetic acid or chlorinated hydrocarbons, such as methylene chloride,chloroform or carbon tetrachloride, can, if necessary, also be used asdiluents.

Suitable catalysts or reaction auxiliaries for carrying out preparationprocess (c) are likewise the catalysts customarily used for suchreactions; acidic catalysts, such as, for example, sulphuric acid, iron(III) chloride or other Lewis acids or acetic anhydride, are preferablyused.

In carrying out preparation process (c), the reaction temperatures canbe varied within a relatively wide range. In general, the reaction iscarried out at between -50° C. and +200° C., preferably between -20° C.and +150° C.

In carrying out preparation process (c), in general 1.0 to 10.0 mols,preferably 1.0 to 5.0 mols, of the electrophilic agent of the formula(VII) and, if appropriate, 0.1 to 10 mols of catalyst or reactionauxiliary are employed per mol of 5-amino-pyrazole of the formula (Ic).The reaction procedure and working-up and isolation of the reactionproducts of formula (I) are carried out in a generally customary manner.

Suitable diluents for carrying out preparation process (d) are likewiseinert organic solvents. The solvents mentioned in the case ofpreparation process (b) are preferably used. For the reaction with analkali metal fluoride of the formula (IX), it is also possible to usewater or aqueous mixtures with one of the solvents mentioned in the caseof process (b).

Suitable acid-binding agents for carrying out preparation process (d)are likewise all organic or inorganic bases which can customarily beused. Alkali metal hydroxides, carbonates or bicarbonates, such as, forexample, potassium carbonate or sodium bicarbonate, are preferably used.Tertiary organic bases, such as triethylamine or pyridine, are alsosuitable.

In preparation process (d), the reaction temperatures can likewise bevaried within a wide range. In general, the reaction is carried out atbetween -20° C. and +120° C., preferably between 0° C. and +90° C.

In carrying out preparation process (d), in general 1.0 to 3.0 mols,preferably 1.0 to 2.0 mols, of the amine of the formula (VIII) or thealkali metal fluoride of the formula (IX) and, if appropriate, 1.0 to3.0 mols, preferably 1.0 to 2.0 mols, of acid-binding agent are employedper mol of 4-chlorosulphonyl-5-amino-pyrazole of the formula (Id). Thereaction procedure and working-up and isolation of the reaction productsof the formula (I) are carried out in a customary manner.

Suitable diluents for carrying out preparation process (e) are likewiseinert organic solvents. Alcohols, such as, for example, methanol,ethanol or propanol, are preferably used.

Suitable acid-binding agents for carrying out preparation process (e)are likewise all organic and inorganic bases which can customarily beused. The acid-binding agents mentioned in the case of process (b) arepreferably used.

In carrying out preparation process (e), the reaction temperature canlikewise be varied within a wide range. In general, the reaction iscarried out at between +20° C. and +150° C., preferably between +20° C.and +120° C.

In carrying out preparation process (e), in general 1.0 to 3.0 mols,preferably 1.0 to 2.0 mols, of the hydroxylamine derivatives of theformula (X) and, if appropriate, 1.0 to 3.0 mols of acid-binding agentare employed per mol of the 4-acyl-5-amino-pyrazole of the formula (Ie).The reaction procedure and working-up and isolation of the reactionproducts of the formula (I) are carried out in a generally customarymanner.

Suitable diluents for carrying out preparation process (f) are inertorganic solvents or aqueous systems. The formic acid used as a reactantis preferably used as the diluent, in an appropriate excess and, ifrequired, as a mixture with water.

In carrying out preparation process (f), the reaction temperatures canlikewise be varied within a wide range. In general, the reaction iscarried out at between 0° C. and +150° C., preferably between +20° C.and 130° C.

In carrying out preparation process (f), in general 0.1 to 3 mols,preferably 0.5 to 2 mols, of Raney nickel and in general 10 to 30 mols,preferably 1.0 to 15 mols, of formic acid are employed per mol of4-cyano-5-amino-pyrazole of the formula (XI).

The reaction procedure and working-up and isolation of the reactionproducts of the formula (I) are carried out in a customary manneranalogous to known methods (see, for example, Chem. Pharm. Bull. 24,3120 [1976]).

The active compounds which can be employed according to the inventioncan be used as defoliants, desicants and agents for destroyingbroad-leaved plants, and especially as weedkillers. By weeds, in thebroadest sense, there are to be understood all plants which grow inlocations where they are undesired. Whether the substances which can beused according to the invention act as total or selective herbicidesdepends essentially on the amount used.

The active compounds which can be employed according to the inventioncan be used, for example, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However the use of the active compounds which can be employed accordingto the invention is in no way restricted to these genera, but alsoextends in the same manner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, andfor the selective combating of weeds in annual cultures.

In addition to exhibiting a particularly good general herbicidalactivity, the active compounds of the formula (I) which can be usedaccording to the invention also exhibit substantially improvedselectivity with regard to crop plants in important cultures, and can beemployed as agents for selectively combating weeds both in dicotyledoncultures, such as, for example, cotton plantings, soy beans orgroundnuts, and in monocotyledon cultures, in particular cereals, suchas, for example, wheat.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis, emulsifying agents and/or dispersing agents, and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkyl naphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylene or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-dispersed silicic acid, alumina and silicates;as solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as saw-dust,coconut shells, corn cobs and tobacco stalks; as emulsifying and/orfoam-forming agents there are suitable: for example non-ionic andanionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkylsulphonates, alkylsulphates, arylsulphonates as well asalbumin hydrolysis products; as dispersing agents there are suitable:for example ligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds which can be employed according to the invention,as such or in the form of their formulations, can also be used, forcombating weeds, as mixtures with known herbicides, finishedformulations or tank mixtures being possible.

Suitable herbicides for the mixtures are known herbicides, such as, forexample,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dioneor N-(2-benzothiazolyl)-N,N'-dimethylurea for combating weeds incereals, 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one for combatingweeds in sugarbeet and4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5-(4H)-one forcombating weeds in soy beans. Mixtures withN,N-dimethyl-N'-(3-trifluoromethylphenyl)-urea,N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea,N,N-dimethyl-N'-(4-isopropylphenyl)-urea,4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one,2,4-dichlorophenoxyacetic acid, 2,4-dichlorophenoxypropionic acid,(2-methyl-4-chlorophenoxy)acetic acid,(4-chloro-2-methyl-phenoxy)-propionic acid, chloroacetic acidN-(methoxymethyl)-2,6-dimethylanilide,2-ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)-chloroacetanilide,2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline, and 2-benzyloxyethyl,trimethylsilylmethyl or 2,2-diethoxyethyl2-[4-(3,5-dichloropyrid-2-yloxy)-phenoxy]-propionate are also possible.Surprisingly, some mixtures also exhibit a synergistic action.

Mixtures with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds which can be used according to the invention can beapplied either before or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.001 and 10 kg of active compound perhectare of soil area, preferably between 0.01 and 5 kg per ha.

The examples which follow illustrate the preparation and the use of theactive compounds which can be used according to the invention.

PREPARATION EXAMPLES EXAMPLE 1 ##STR94## Process A

20 mg of disodium ethylenediamine-tetraacetate (=Titriplex III) in 150ml of methanol are added dropwise to 24.5 g (0.1 mol) of2,6-dichloro-4-trifluoromethylphenylhydrazine at the reflux temperature,and 25 ml (27.6 g/0.3 mol) of 2-chloroacrylonitrile are added. When theaddition is complete, heating is continued for a further 8 hours at thereflux temperature, after which 9 ml (0.16 mol) of 96% strengthsulphuric acid are added dropwise and heating is continued for a further6 hours at the reflux temperature. 33.5 g (0.3 mol) of anhydrous sodiumcarboante are added to the cooled reaction mixture. After 4 hours, thesolvent is removed in vacuo, the residue is taken up in 500 ml of water,and the solution is stirred for 10 hours at room temperature. Theprecipitate which separates out is filtered off, rinsed with water anddried in vacuo at 50° C.

28.5 g (96% of theory) of5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-pyrazole of meltingpoint 103°-105° C. are obtained.

EXAMPLE 2 ##STR95## Process B

5 ml (5.3 g/0.05 mol) of 98 % strength propionyl chloride and then 5 ml(5.0 g/0.063 mol) of anhydrous pyridine are added in succession to 13.2g (0.05 mol) of 5-amino-1-(2,4,6-trichlorophenyl)-pyrazole in 100 ml ofdichloromethane at room temperature, while stirring. During theaddition, the temperature increases to 40° C. When the addition iscomplete, stirring is continued for a further 16 hours at roomtemperature, 50 ml of dichloromethane are added, the mixture is washedwith twice 100 ml of water, 100 ml of saturated sodium bicarbonatesolution and 100 ml of sodium chloride solution and is dried overmagnesium sulphate, and the solvent is removed in vacuo. The solidresidue is washed with a small amount of hexane and is dried.

12.5 g (81% of theory) of5-propionamido-1-(2,4,6-trichlorophenyl)-pyrazole of melting point 125°C. are obtained.

EXAMPLE 3 ##STR96## Process C

2 ml (2.17 g/0.021 mol) of acetic anhydride and then 0.9 ml (1.3 g/0.02mol) of 98% strength nitric acid are added in succession to 6.4 g (0.02mol) of 5-propionamido-1-(2,3,4-trichlorophenyl)-pyrazole in 20 ml ofglacial acetic acid at 10° C. When the addition is complete, the mixtureis stirred for 16 hours at 25° C. To work up the mixture, it isevaporated down in vacuo, the residue is taken up in 20 ml of diethylether, the solution is washed three times with a total of 50 to 100 mlof concentrated sodium bicarbonate solution and twice with 50 ml ofsaturated sodium chloride solution, the solvent is removed in a vacuumfrom a water pump, and the solid residue is washed with a small amountof water and dried in a high vacuum at 30° C. to 40° C. 5.5 g (76% oftheory) of 4-nitro-5-propionamido-1-(2,3,4-trichlorophenyl)-pyrazole ofmelting point 79°-81° C. are obtained.

EXAMPLE 4 ##STR97## Process C

A solution of 1.6 g (0.02 mol) of bromine in 5 ml of glacial acetic acidis added dropwise to 2.6 g (0.01 mol) of5-amino-1-(2,3,4-trichlorophenyl)-pyrazole in 10 ml of glacial aceticacid at 20° C., while stirring. When the addition is complete, stirringis continued for a further 3 hours at 20° C., after which 30 ml of waterand 3 g (0.022 mol) of sodium acetate trihydrate are added, stirring iscontinued for a further hour, and the crystalline precipitate isfiltered off under suction, washed with water and dried at 50° C. to 60°C. in vacuo. 3.2 g (94% of theory) of5-amino-4-bromo-1-(2,3,6-trichlorophenyl)-pyrazole of melting point 129°C. are obtained.

EXAMPLE 5 ##STR98## Process C

1.2 g (0.009 mol) of sulfuryl chloride are added dropwise to 2.7 g(0.0085 mol) of 5-propionamide-1-(2,3,4-trichlorophenyl)-pyrazole in 20ml of dichloromethane at 0° C. to 5° C. When the addition is complete,stirring is continued for a further 16 hours at room temperature, themixture is diluted with 30 ml of dichloromethane, washed several timeswith water, saturated sodium bicarbonate solution and saturated sodiumchloride solution, dried over sodium sulphate and evaporated down invacuo, and the residue is dried at 50° C. in a high vacuum. 2.5 g (83%of theory) of 4-chloro-5-propionamido-1-(2,3,4-trichlorophenyl)-pyrazoleof melting point 122° C. are obtained.

EXAMPLE 6 ##STR99## Process F

12 g (0.042 mol) of5-amino-4-cyano-1-(2-chloro-4-trifluoromethoxy-phenyl)-pyrazole areboiled under reflux with 5 g of Raney nickel in 50 ml of 75% strengthaqueous formic acid for 1 hour; the still warm solution is filteredunder suction, the residue is rinsed with water, the filtrate isextracted several times with ether, and the combined ether phases arewashed with saturated sodium bicarbonate solution, dried over sodiumsulphate and evaporated down in vacuo. 8.0 g (62% of theory) of5-amino-1-(2-chloro-4-trifluoromethoxy-phenyl)-4-formylpyrazole areobtained in the form of an oil.

    ______________________________________                                        .sup.1 H-NMR                                                                             δ [ppm] = 5.7                                                                       (2, 2H) - singlet                                                 7.3-7.6     (m, 3H) - multiplet                                               7.85        (s, 1H) - singlet                                                 9.6         (s, 1H) - singlet                                      ______________________________________                                    

EXAMPLE 7 ##STR100## Process A

6.3 g (0.03 mol) of 2,3,4-trichlorophenylhydrazine, 5.8 g (0.025 mol) ofethoxymethylene-diethylphosphonoacetonitrile and 1 g of (0.012 mol) ofanhydrous sodium acetate are suspended in 10 ml of glacial acetic acid,and the suspension is stirred for 48 hours at room temperature. 50 ml ofdichloromethane and 100 ml of water are added to the reaction mixture.The organic phase is separated off and washed once in each case with 50ml of saturated sodium bicarbonate solution and 30 ml of saturatedsodium chloride solution. After the solution has been dried overmagnesium sulphate, the solvent is distilled off in vacuo, the oilyresidue is dissolved in 15 ml of ethoxyethanol, and the solution isheated under reflux for 5 hours. It is then cooled to room temperature,30 ml of water are added to the solution and stirring is continued untilthe initially oily precipitate crystallizes. The slightly yellowcrystals are filtered off under suction, washed with water and dried invacuo at 50°- 60° C.

5.6 g (46.8% of theory) of5-amino-4-diethylphosphono-1-(2,3,4-trichlorophenyl)-pyrazole of meltingpoint 114° C. are obtained.

Preparation of the Starting Compound ##STR101##

35.4 g (0.2 mol) of diethylphosphonoacetonitrile (see Houben-Weyl"Methoden der organischen Chemie" (Methods of organic chemistry), VolumeE2, page 345, 4th Edition, Thieme Verlag Stuttgart, 1982), 42 ml (0.45mol) of acetic anhydride and 56 ml (0.34 mol) of triethyl o-formate arestirred for 2 hours at 110° C. Thereafter, the low-boiling compounds aredistilled off over a short column under atmospheric pressure, the bottomtemperature increasing to 140° C. This temperature is maintained for afurther 4 hours, and the unreacted starting compounds are then distilledoff, first under a vacuum from a water pump and then under a vacuum froman oil pump. 20.5 g (44% of theory) ofethoxymethylene-diethylphosphonoacetonitrile remain as an oil at thebottom.

    ______________________________________                                        .sup.1 H-NMR (CDCl.sub.3) =                                                                  δ = 7.63 ppm                                                                       (d, 1H) - doublet                                                  4.32 ppm   (q, 2H) - quartet                                                  4.15 ppm   (m, 4H) - multiplet                                                1.45-1.35 ppm                                                                            (m, 9H) - multiplet                                 ______________________________________                                    

The following compounds of the general formula (I) are obtained in acorresponding manner and in accordance with the general preparationdata.

                                      TABLE 2                                     __________________________________________________________________________     ##STR102##                                         (I)                       Example                                       Melting                         No.  R.sup.1  R.sup.2    R.sup.3                                                                            R.sup.4                                                                           R.sup.5                                                                         R.sup.6                                                                             R.sup.7                                                                         R.sup.8                                                                         point (°C.)              __________________________________________________________________________    8    NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H Cl    H Cl                                                                               54° C.                  9    NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H CF.sub.3                                                                            H Cl                                                                               48° C.                  10   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H CF.sub.3                                                                            H H 115° C.                                                                (decomposition)                 11   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H SCF.sub.3                                                                           H Cl                                                                              96-99°  C.               12   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H OCF.sub.3                                                                           H H  65° C.                  13   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  Cl                                                                              CF.sub.3                                                                            Cl                                                                              Cl                                                                              54-60° C.                14   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    CF.sub.3                                                                          H Cl    H H                                 15   NO.sub.2 H          H    Cl  H Cl    H Cl                                                                              218° C.                  16   NO.sub.2 CH.sub.3 CO                                                                              H    Cl  H CF.sub.3                                                                            H Cl                                                                               50° C.                  17   NO.sub.2 CH.sub.3 CO                                                                              H    Cl  H SCF.sub.3                                                                           H Cl                                                                              58-61° C.                18   NO.sub.2 CH.sub.3 (CH.sub.2).sub.2 CO                                                             H    Cl  H CF.sub.3                                                                            H Cl                                                                               44° C.                  19   NO.sub.2 CH.sub.3 OCO                                                                             H    Cl  H CF.sub.3                                                                            H Cl                                                                              141-43° C.               20   NO.sub.2 ClCH.sub.2 CO                                                                            H    Cl  H CF.sub.3                                                                            H Cl                                                                              130-33° C.               21   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H Cl    H H  63° C.                  22   H        H          H    Cl  H Cl    H Cl                                                                              113° C.                  23   H        H          H    Cl  H CF.sub.3                                                                            H H 88-92°  C.               24   H        H          H    Cl  H SCF.sub.3                                                                           H Cl                                                                               79° C.                  25   H        H          H    Cl  Cl                                                                              Cl    H H 152° C.                  26   H        H          H    Cl  Cl                                                                              CF.sub.3                                                                            Cl                                                                              Cl                                                                              103-10° C.               27   H        H          H    Cl  H OCF.sub.3                                                                           H H 73-76° C.                28   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  Cl                                                                              Cl    H H  55° C.                  29   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  H CF.sub.3                                                                            H H 106-10° C.               30   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  H SCF.sub.3                                                                           H Cl                                                                              136° C.                  31   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  H CF.sub.3                                                                            H Cl                                                                              146° C.                  32   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  H OCF.sub.3                                                                           H H Oil                             33   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  Cl                                                                              CF.sub.3                                                                            Cl                                                                              Cl                                                                              154-58° C.               34   H        C.sub.2 H.sub.5 CO                                                                       H    CF.sub.3                                                                          H Cl    H H Oil                             35   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  H Cl    H H Oil                             36   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  H SO.sub. 2 CF.sub.2 Cl                                                               H Cl                                                                              134° C.                  37   H        CH.sub.3 CO                                                                              C.sub.2 H.sub.5 CO                                                                 Cl  Cl                                                                              Cl    H H 142° C.                  38   H        CH.sub.3 CO                                                                              CH.sub.3 CO                                                                        Cl  Cl                                                                              Cl    H H 142° C.                  39   H        CH.sub.3 OCO                                                                             H    Cl  H CF.sub.3                                                                            H Cl                                                                              123-126° C.              40   H        CH.sub.3 CO                                                                              H    Cl  H CF.sub.3                                                                            H Cl                                                                              173-76° C.               41   H        CH.sub.3 CO                                                                              H    Cl  H SCF.sub.3                                                                           H Cl                                                                              131° C.                  42   H        CH.sub.3 (CH.sub.2).sub.2 CO                                                             H    Cl  H CF.sub.3                                                                            H Cl                                                                              128-31° C.               43   H        ClCH.sub.2 CO                                                                            H    Cl  H CF.sub.3                                                                            H Cl                                                                              149-50° C.               44   Br       C.sub.2 H.sub.5 CO                                                                       H    Cl  Cl                                                                              Cl    H H  78° C.                  45   I        H          H    Cl  Cl                                                                              Cl    H H 162° C.                  46                                                                                  ##STR103##                                                                            H          H    Cl  Cl                                                                              Cl    H H 156-59° C.               47   HONCH    H          H    Cl  H OCF.sub.3                                                                           H H 180° C.                  48                                                                                  ##STR104##                                                                            C.sub.2 H.sub.5 CO                                                                       H    Cl  Cl                                                                              Cl    H H Oil                             49   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H SO.sub.2 CCl.sub.2 F                                                                H Cl                                                                              156-58° C.               50   NO.sub.2 H          H    Cl  H CF.sub.3                                                                            H Cl                                                                              189-90° C.               51   NO.sub.2 H          H    Cl  H SO.sub.2 CCl.sub.2 F                                                                H Cl                                                                              208-09° C.               52   H        C.sub.2 H.sub.5 CO                                                                       CH.sub.3                                                                           Cl  H Cl    H Cl                                                                              150-51                          53   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       CH.sub.3                                                                           Cl  H Cl    H Cl                                                                              192-98                          54   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  H SCF.sub.3                                                                           H H Oil                             55   H                                                                                       ##STR105##                                                                              H    Cl  H CF.sub.3                                                                            H Cl                                                                              69-71                           56   H        C.sub.11 H.sub.23 CO                                                                     H    Cl  H CF.sub.3                                                                            H Cl                                                                              63-66                           57   SCCl.sub.2 F                                                                           H          H    Cl  H Cl    H Cl                                                                              102                             58   SCCl.sub.2 F                                                                           C.sub.2 H.sub.5 CO                                                                       H    Cl  H Cl    H Cl                                                                              128-29                          59   NO.sub. 2                                                                              H          H    Cl  H OCF.sub.3                                                                           H H  50                             60   NO.sub.2                                                                                ##STR106##                                                                              H    Cl  H CF.sub.3                                                                            H Cl                                                                              165-68                          61   No.sub.2 C.sub.11 H.sub.23 CO                                                                     H    Cl  H CF.sub.3                                                                            H Cl                                                                              60-70                           62   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H SCF.sub.3                                                                           H H 90-93                           63   Cl       C.sub.2 H.sub.5 CO                                                                       H    Cl  H CF.sub.3                                                                            H Cl                                                                              63-65                           64   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  H OCF.sub.3                                                                           H Cl                                                                              50-56                           65   SOCCl.sub.2 F                                                                          C.sub.2 H.sub.5 CO                                                                       H    Cl  H Cl    H Cl                                                                              143-46                          66   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H SO.sub.2 CF.sub.3                                                                   H H 60-64                           67   SO.sub.2 CCl.sub.2 F                                                                   C.sub.2 H.sub.5 CO                                                                       H    Cl  H Cl    H Cl                                                                              136-39                          68   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  Cl                                                                              CF.sub.3                                                                            H Cl                                                                              129-32                          69   NO       H          H    Cl  H CF.sub.3                                                                            H Cl                                                                              227                             70   NO.sub.2 H          H    Cl  H SO.sub.2 CF.sub.3                                                                   H H 68-70                           71   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H OCF.sub.3                                                                           H Cl                                                                              130-35                          72   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H SO.sub.2 CF.sub.3                                                                   H Cl                                                                              132-34                          73   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  Cl                                                                              CF.sub.3                                                                            H Cl                                                                              50-52                           74   (C.sub.2 H.sub.5 O).sub.2 P(O)                                                         H          H    Cl  H CF.sub.3                                                                            H Cl                                                                              Oil                             75   NO.sub.2 H          H    Cl  H SCF.sub.3                                                                           H H 56-60                           76   NO.sub.2 H          H    Cl  H SCF.sub.3                                                                           H Cl                                                                              145-49                          77   NO.sub.2 H          H    Cl  H OCF.sub.3                                                                           H Cl                                                                              206-08                          78   NO.sub.2 H          H    Cl  H SO.sub.2 CF.sub.3                                                                   H Cl                                                                              249-53                          79   NO.sub.2 H          H    Cl  Cl                                                                              CF.sub.3                                                                            H Cl                                                                              78-85                           80   H        CH.sub.3 NHCO                                                                            H    Cl  H CF.sub.3                                                                            H Cl                                                                              178-82                          81   H                                                                                       ##STR107##                                                                              H    Cl  H CF.sub.3                                                                            H Cl                                                                              65-67                           82   H        (CH.sub.3).sub.2 NCO                                                                     H    Cl  H CF.sub.3                                                                            H Cl                                                                              137-38                          83   H        C.sub.2 H.sub. 5 CO                                                                      H    Cl  Cl                                                                              Cl    H Cl                                                                              62-67                           84   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  Cl                                                                              Cl    H Cl                                                                              60-67                           85   H        ClCH.sub.2 CH.sub.2CO                                                                    H    Cl  H CF.sub.3                                                                            H Cl                                                                              120-24                          86   NO.sub.2 CH.sub.3 NHCO                                                                            H    Cl  H CF.sub.3                                                                            H Cl                                                                              212-14                          87   NO.sub.2                                                                                ##STR108##                                                                              H    Cl  H CF.sub.3                                                                            H Cl                                                                              48-52                           88   NO.sub.2 H          H    Cl  Cl                                                                              Cl    H Cl                                                                              83-89                           89   NO.sub.2 H          CH.sub.3                                                                           Cl  H Cl    H Cl                                                                              167-75                          90   H        H          CH.sub.3                                                                           Cl  H Cl    H Cl                                                                              186-88                          91   H        ClCH.sub.2CO                                                                             H    Cl  H CF.sub.3                                                                            H H 103-05                          92   H        ClCH.sub.2CO                                                                             H    Cl  H OCF.sub.3                                                                           H H 84-87                           93   NO.sub.2 H          H    Cl  H CF.sub.3                                                                            H H 55-58                           94   NO.sub.2 ClCH.sub.2 CH.sub.2CO                                                                    H    Cl  H CF.sub.3                                                                            H Cl                                                                              135-40                          95   NO.sub.2 ClCH.sub.2CO                                                                             H    Cl  H OCF.sub.3                                                                           H H Oil                             96   NO.sub.2 ClCH.sub.2 CO                                                                            H    Cl  H CF.sub.3                                                                            H H 111-13                          97   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  F CF.sub.3                                                                            F Cl                                                                              121-23                          98   NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  F CF.sub.3                                                                            F Cl                                                                              135-37                          99   H        C.sub.2 H.sub.5 CO                                                                       H    Cl  F Cl    F Cl                                                                              190-93                          100  NO.sub.2 H          CH.sub.3                                                                           Cl  H CF.sub.3                                                                            H H 120-23                          101  NO.sub.2 C.sub.2 H.sub.5 CO                                                                       CH.sub.3                                                                           Cl  H CF.sub.3                                                                            H Cl                                                                              140-54                          102  NO.sub.2 H          H    Cl  F CF.sub.3                                                                            F Cl                                                                              158-65                          103  NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  F Cl    F Cl                                                                              130-33                          104  NO.sub.2 CH.sub.2CHCO                                                                             H    Cl  H CF.sub.3                                                                            H Cl                                                                              55-65                           105  NO.sub.2 H          H    Cl  F Cl    F Cl                                                                              210-20                          106  H        HCO        H    Cl  H CF.sub.3                                                                            H Cl                                                                              144-50                          107  NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H OCH.sub.3                                                                           H Cl                                                                              165-74                          108  NO.sub.2 HCO        H    Cl  H CF.sub.3                                                                            H Cl                                                                              144-50                          109  NO.sub.2 H          CH.sub.3                                                                           Cl  H CF.sub.3                                                                            H Cl                                                                              120-40                          110  SCCl.sub.2 F                                                                           H          H    Cl  H CF.sub.3                                                                            H Cl                                                                               99-105                         111  SOCCl.sub.2 F                                                                          H          H    Cl  H CF.sub.3                                                                            H Cl                                                                              55-62                           112  H        CH.sub.3 CO                                                                              H    Cl  Cl                                                                              CF.sub.3                                                                            H Cl                                                                              158-62                          113  SO.sub.2 CCl.sub.2 F                                                                   H          H    Cl  H CF.sub.3                                                                            H Cl                                                                              135-38                          114  NO.sub.2 CH.sub.3 CO                                                                              H    Cl  Cl                                                                              CF.sub.3                                                                            H Cl                                                                              124-33                          115  H        CH.sub.3 CO                                                                              H    Cl  H CF.sub.3                                                                            H H 50-52                           116  NO.sub.2 CH.sub.3 CO                                                                              H    Cl  H CF.sub.3                                                                            H H 62-65                           117  H        H          CH.sub.3                                                                           Cl  H CF.sub.3                                                                            H Cl                                                                              135-37                          118  H                                                                                       ##STR109##                                                                              H    Cl  H CF.sub.3                                                                            H Cl                                                                              62-64                           119  NO.sub.2 ClCH.sub.2 CH.sub.2 CH.sub.2 CO                                                          H    Cl  H CF.sub.3                                                                            H Cl                                                                              60-63                           120  NO.sub.2                                                                                ##STR110##                                                                              H    Cl  H CF.sub.3                                                                            H Cl                                                                              157-65                          121  H        C.sub. 2 H.sub.5 CO                                                                      H    Cl  H Br    H H 86-88                           122  H        H          H    Br  H Br    H Br                                                                              141-43                          123  H        C.sub.2 H.sub.5 CO                                                                       H    Br  H Br    H Br                                                                              147-50                          124  H        H          H    Cl  H Br    H Cl                                                                              102                             125  H        H          H    Br  H Cl    H Br                                                                               98                             126  NO.sub.2 H          H    Cl  H Br    H H 95-98                           127  H        H          H    I   H I     H H 138-40                          128  NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Br  H Br    H Br                                                                              92-94                           129  H        C.sub.2 H.sub.5 CO                                                                       H    Br  H Cl    H Br                                                                              138-40                          130  H        C.sub.2 H.sub.5 CO                                                                       H    Cl  H Br    H Cl                                                                              142-48                          131  H        H          H    Br  H Cl    H Cl                                                                              105-07                          132  NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Br  H Cl    H Br                                                                              146-48                          133  H        ClCH.sub.2 CO                                                                            H    Br  H Cl    H Br                                                                              127-30                          134  H        H          H    Br  H F     H H 58-60                           135  NO.sub.2 H          H    Br  H Cl    H Br                                                                              230                             136  H        H          H    Br  Cl                                                                              Cl    H Br                                                                              120-25                          137  NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Cl  H Br    H Cl                                                                               94                             138  NO.sub.2 H          H    Cl  H Br    H Cl                                                                              198                             139  H        C.sub.2 H.sub.5 CO                                                                       H    Br  H Br    H Cl                                                                              114-18                          140  NO.sub.2 ClCH.sub.2 CO                                                                            H    Br  H Cl    H Br                                                                              115-20                          141  H        C.sub.2 H.sub.5 CO                                                                       H    I   H I     H H Oil                             142  H        H          H    Br  Cl                                                                              Br    H Cl                                                                              170                             143  NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Br  H Br    H Cl                                                                              89-93                           144  NO.sub.2 H          H    Br  H Br    H Cl                                                                              208-10                          145  H        C.sub.2 H.sub.5 CO                                                                       H    Br  Cl                                                                              Cl    H Br                                                                              165                             146  H        C.sub.2 H.sub.5 CO                                                                       H    Br  Cl                                                                              Br    H Cl                                                                              140-50                          147  NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    I   H I     H H 55-60                           148  NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Br  Cl                                                                              Cl    H Br                                                                              130-40                          149  NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Br  H F     H H 72-74                           150  NO.sub.2 C.sub.2 H.sub.5 CO                                                                       H    Br  H OCF.sub.3                                                                           H H 83-85                           151  Br       H          H    Cl  H Cl    H Cl                                                                              119                             152  SCH.sub.3                                                                              H          H    Cl  H Cl    H Cl                                                                              114                             153  Br       H          H    OCH.sub.3                                                                         H Cl    H Cl                                                                              67-70                           154  SCH.sub.3                                                                              C.sub.2 H.sub.5 CO                                                                       H    Cl  H Cl    H Cl                                                                              92-95                           155  SO.sub.2 CH.sub.3                                                                      C.sub.2 H.sub.5 CO                                                                       H    Cl  H Cl    H Cl                                                                              146-50                          156  CHO      H          H    Cl  H OCF.sub.3                                                                           H H Oil                             157  CHO      C.sub.2 H.sub.5 CO                                                                       H    Cl  H OCF.sub.3                                                                           H H Oil                             158  CHNOCH.sub.3                                                                           H          H    Cl  H OCF.sub.3                                                                           H H 138-39                          159  H        ClCH.sub.2 CH.sub.2 CH.sub.2 CO                                                          H    Cl  H CF.sub.3                                                                            H Cl                                                                              Oil                             160  NO.sub.2 Cl.sub.2 CHCO                                                                            H    Cl  H CF.sub.3                                                                            H Cl                                                                              110-114                         161  NO.sub.2 ClCH.sub.2 CO                                                                            H    Cl  H Cl    H H Ol                              __________________________________________________________________________

The following compounds of the formula (I') listed in tables 3 and 4 areobtained in a corresponding manner and in accordances with the generalpreparation data: ##STR111##

                                      TABLE 3                                     __________________________________________________________________________    R.sup.1 = S(O).sub.nR.sup.9                                                   Ex. No.                                                                            R.sup.2                                                                         R.sup.9  R.sup.3                                                                             Ar          n melting point/°C.                  __________________________________________________________________________    162  H CF.sub.2 Cl                                                                            H                                                                                               2 148-150                                   163  H CF.sub.2 Cl                                                                            H                                                                                    ##STR112## 0 96-98                                     164  H CF.sub.2 Cl                                                                            H                                                                                    ##STR113## 1 110-115                                   165  H CF.sub.3 H                                                                                    ##STR114## 0 126                                       166  H CF.sub.3 H                                                                                    ##STR115## 2 144                                       167  H CCl.sub.2 F                                                                            H                                                                                    ##STR116## 0 O l                                       168  H CF.sub.3 H                                                                                    ##STR117## 1 82-88                                     169  H CCl.sub.2 F                                                                            H                                                                                    ##STR118## 0 114-118                                   170  H CCl.sub.2 F                                                                            H                                                                                    ##STR119## 0 110-115                                   171  H CCl.sub.2 F                                                                            H                                                                                    ##STR120## 0 73                                        172  H CCl.sub.2 F                                                                            H                                                                                    ##STR121## 2 145                                       173  H CCl.sub.2 F                                                                            H                                                                                    ##STR122## 1  99-112                                   174  H CCl.sub.2 F                                                                            H                                                                                    ##STR123## 2 132                                       175  H CCl.sub.2 F                                                                            H                                                                                    ##STR124## 0 119                                       176  H CF.sub.2 Cl                                                                            H                                                                                    ##STR125## 0 116-118                                   177  H CF.sub.2 Cl                                                                            H                                                                                    ##STR126## 1 117-118                                   178  H CCl.sub.2 F                                                                            H                                                                                    ##STR127## 0 84-86                                     179  H CF.sub.2 Cl                                                                            H                                                                                    ##STR128## 0 87-88                                     180  H                                                                                ##STR129##                                                                            H                                                                                    ##STR130## 0 150-156                                   181  H CCl.sub.2 F                                                                            H                                                                                    ##STR131## 2 80-85                                     182  H CCl.sub.2 F                                                                            H                                                                                    ##STR132## 2 165-168                                   183  H                                                                                ##STR133##                                                                            H                                                                                    ##STR134## 2 170-175                                   184  H CCl.sub.2 F                                                                            H                                                                                    ##STR135## 0 125-133                                   185  H CCl.sub.2 F                                                                            H                                                                                    ##STR136## 1 102-107                                   186  H CCl.sub.2 F                                                                            H                                                                                    ##STR137## 1 70-77                                     187  H CCl.sub.2 F                                                                            H                                                                                    ##STR138## 0 134-136                                   188  H CCl.sub.2 F                                                                            H                                                                                    ##STR139## 0 70                                        189  H CF.sub.2 Cl                                                                            H                                                                                    ##STR140## 2 112-120                                   190  H CCl.sub.2 F                                                                            H                                                                                    ##STR141## 0 Ol                                        191  H CClF.sub.2                                                                             H                                                                                    ##STR142## 0 103-108                                   192  H CClF.sub.2                                                                             H                                                                                    ##STR143## 0 119-122                                   193  H CClF.sub.2                                                                             H                                                                                    ##STR144## 2 128-133                                   194  H CClF.sub.2                                                                             H                                                                                    ##STR145## 1 78-98                                     195  H CClF.sub.2                                                                             H                                                                                    ##STR146## 2  98-103                                   196  H CCl.sub.2 F                                                                            H                                                                                    ##STR147## 0 88-90                                     197  H CCl.sub.2 F                                                                            H                                                                                    ##STR148## 0 80-85                                     198  H CCl.sub.2 F                                                                            H                                                                                    ##STR149## 1 106-111                                   199  H CCl.sub.2 F                                                                            H                                                                                    ##STR150## 0 109-113                                   200  H CCl.sub.2 F                                                                            H                                                                                    ##STR151## 0 113-116                                   201  H CCl.sub.2 F                                                                            H                                                                                    ##STR152## 2 80                                        202  H CF.sub.3 H                                                                                    ##STR153## 0 84-87                                     203  H CClF.sub.2                                                                             H                                                                                    ##STR154## 1 63-70                                     204  H CF.sub.3 H                                                                                    ##STR155## 0 94                                        205  H CCl.sub.2 F                                                                            CH.sub.3                                                                             ##STR156## 2 144-150                                   206  H CCl.sub.2 F                                                                            H                                                                                    ##STR157## 1 70-72                                     207  H CCl.sub.2 F                                                                            CH.sub.3                                                                             ##STR158## 1 141-146                                   208  H CF.sub.3 COCH.sub.3                                                                           ##STR159## 1 103                                       209  H CF.sub.3 H                                                                                    ##STR160## 0 131-132                                   210  H CF.sub.3 H                                                                                    ##STR161## 0 82-83                                     211  H CCl.sub.2 F                                                                            H                                                                                    ##STR162## 0 137-139                                   212  H CF.sub.3 H                                                                                    ##STR163## 1 55-57                                     213  H CCl.sub.2 F                                                                            H                                                                                    ##STR164## 1 59-66                                     214  H CF.sub.3 H                                                                                    ##STR165## 1 133                                       215  H CCl.sub.2 F                                                                            H                                                                                    ##STR166## 2 107-112                                   216  H CF.sub.3 H                                                                                    ##STR167## 2 110-116                                   217  H CF.sub.3 H                                                                                    ##STR168## 2 108-111                                   218  H CCl.sub.2 F                                                                            H                                                                                    ##STR169## 0 116-118                                   219  H CCl.sub.2 F                                                                            H                                                                                    ##STR170## 0 95-97                                     220  H                                                                                ##STR171##                                                                            H                                                                                    ##STR172## 0 121                                       221  H CCl.sub.2 F                                                                            H                                                                                    ##STR173## 0 150-152                                   222  H CCl.sub.2 F                                                                            H                                                                                    ##STR174## 0 81-83                                     223  H CCl.sub.2 F                                                                            H                                                                                    ##STR175## 0 154-156                                   224  H CClF.sub.2                                                                             H                                                                                    ##STR176## 1 92-99                                     225  H CF.sub.3 H                                                                                    ##STR177## 0 122-124                                   226  H CF.sub.3 H                                                                                    ##STR178## 0 109-114                                   227  H CClF.sub.2                                                                             H                                                                                    ##STR179## 2 125-132                                   228  H CF.sub.3 CH.sub.3                                                                             ##STR180## 1 125-127                                   229  H CCl.sub.2 F                                                                            COCH.sub.3                                                                           ##STR181## 1 208-210                                   230  H CCl.sub.2 F                                                                            CH(CH.sub.3).sub.2                                                                   ##STR182## 2 Ol                                        231  H CCl.sub.2 F                                                                            COCH.sub.3                                                                           ##STR183## 0 166-169                                   232  H CF.sub.3 H                                                                                    ##STR184## 0 127-128                                   233  H CCl.sub.2 F                                                                            COCH.sub.3                                                                           ##STR185## 2 164-165                                   234  H CF.sub.3 H                                                                                    ##STR186## 2 135-136                                   235  H CH(CH.sub.3).sub.2                                                                     H                                                                                    ##STR187## 1 60-65                                     236  H CH.sub.3 H                                                                                    ##STR188## 0 92                                        237  H C.sub.2 H.sub.5                                                                        H                                                                                    ##STR189## 0 67-68                                     238  H CH(CH.sub.3).sub.2                                                                     H                                                                                    ##STR190## 0 82-83                                     239  H C.sub.2 H.sub.5                                                                        H                                                                                    ##STR191## 1 57-61                                     240  H C.sub.2 H.sub.5                                                                        H                                                                                    ##STR192## 2 130                                       241  H CH(CH.sub.3).sub.2                                                                     H                                                                                    ##STR193## 2 142                                       242  H CH.sub.3 H                                                                                    ##STR194## 0 105                                       243  H C.sub.2 H.sub.5                                                                        H                                                                                    ##STR195## 0 85                                        244  H CH.sub.3 H                                                                                    ##STR196## 0 110                                       245  H C.sub.2 H.sub.5                                                                        H                                                                                    ##STR197## 0 72-73                                     246  H CH(CH.sub.3).sub.2                                                                     H                                                                                    ##STR198## 0 Oil                                       247  H                                                                                ##STR199##                                                                            H                                                                                    ##STR200## 0 155                                       248  H                                                                                ##STR201##                                                                            H                                                                                    ##STR202## 2 178                                       249  H CH.sub.3 H                                                                                    ##STR203## 0 90                                        250  H C.sub.2 H.sub.5                                                                        H                                                                                    ##STR204## 0 79                                        251  H CH.sub.3 H                                                                                    ##STR205## 1 146                                       252  H CH.sub.3 H                                                                                    ##STR206## 2 124                                       253  H C.sub.2 H.sub.5                                                                        H                                                                                    ##STR207## 1 108-110                                   254  H C.sub.2 H.sub.5                                                                        H                                                                                    ##STR208## 2 129                                       255  H CH(CH.sub.3).sub.2                                                                     H                                                                                    ##STR209## 0 80                                        256  H CF.sub.2 CHFCl                                                                         H                                                                                    ##STR210## 0 73                                        257  H CF.sub.3 H                                                                                    ##STR211## 0 110-111                                   258  H CCl.sub.2 F                                                                            H                                                                                    ##STR212## 0 106-110                                   __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________     ##STR213##                                                 (I')              Ex.                                                                           No.                                                                              R.sup.1   R.sup.2     R.sup.3                                                                              R.sup.4                                                                           R.sup.5                                                                           R.sup.6                                                                             R.sup.7                                                                         R.sup.8                                                                          melting                                                                       point/°C.           __________________________________________________________________________    259                                                                              NO.sub.2  H           i-C.sub.3 H.sub.7                                                                    Cl  H   Cl    H Cl 152-4                      260                                                                              NO.sub.2  H           C.sub.4 H.sub.9                                                                      Cl  H   Cl    H Cl  74                        261                                                                              NO.sub.2  H           C.sub.3 H.sub.7                                                                      Cl  H   Cl    H Cl 110                        262                                                                              H         H           H      Cl  OCF.sub.3                                                                         Cl    H H   76                        263                                                                              H         COCHCl.sub.2                                                                              H      Cl  H   SCF.sub.3                                                                           Cl                                                                              Cl 146                        264                                                                              H         COCHCl.sub.2                                                                              H      Cl  OCF.sub.3                                                                         Cl    H H  142                        265                                                                              H         COCH.sub.2 Cl                                                                             H      Cl  H   OCF.sub.3                                                                           Cl                                                                              Cl 107                        266                                                                              H         COCH.sub.2 Cl                                                                             H      Cl  H   SCF.sub.3                                                                           Cl                                                                              Cl 103                        267                                                                              H         COC.sub.2 H.sub.5                                                                         H      Cl  H   OCF.sub.3                                                                           Cl                                                                              Cl  48-53                     268                                                                              H         COC.sub.2 H.sub.5                                                                         H      Cl  H   SCF.sub.3                                                                           Cl                                                                              Cl 100-106                    269                                                                              NO.sub.2  COCH.sub.2 Cl                                                                             H      Cl  H   OCF.sub.3                                                                           Cl                                                                              Cl  38-40                     270                                                                              NO.sub.2  COCH.sub.2 Cl                                                                             H      Cl  H   SCF.sub.3                                                                           Cl                                                                              Cl 103-105                    271                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Cl  H   OCF.sub.3                                                                           Cl                                                                              Cl  80                        272                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Cl  H   SCF.sub.3                                                                           Cl                                                                              Cl .sup.1 H-NMR:                                                                 δ=1,1                                                                   (3H, t)                    273                                                                              NO.sub.2  H           H      Cl  H   SCF.sub.3                                                                           Cl                                                                              Cl 147                        274                                                                              NO.sub.2  COCHCl.sub.2                                                                              H      Cl  OCF.sub.3                                                                         Cl    H H  136                        275                                                                              NO.sub.2  H           H      Cl  H   OCF.sub.3                                                                           Cl                                                                              Cl 163                        276                                                                              NO.sub.2  H           H      Cl  OCF.sub.3                                                                         Cl    H H  110                        277                                                                              NO.sub.2  H           C.sub.3 H.sub.7                                                                      Cl  H   CF.sub.3                                                                            H H   98                        278                                                                              H         COCHClCH.sub.3                                                                            H      Cl  H   OCF.sub.3                                                                           H H   74-77                     279                                                                              H         COCH.sub.2 Cl                                                                             H      Cl  H   Cl    H H   99-104                    280                                                                              NO.sub.2  COCHClCH.sub.3                                                                            H      Cl  H   OCF.sub.3                                                                           H H   92                        281                                                                              NO.sub.2  H           H      Cl  H   Cl    H Cl 158-61                     282                                                                              NO.sub.2  H           i-C.sub.3 H.sub.7                                                                    Cl  H   CF.sub.3                                                                            H H   96                        283                                                                              NO.sub.2  H           C.sub.3 H.sub.7                                                                      Cl  H   SCF.sub.3                                                                           Cl                                                                              Cl  96                        284                                                                              CHO       H           H      Cl  H   Cl    H H  128                        285                                                                              NO.sub.2  H           i-C.sub.3 H.sub.7                                                                    Cl  H   CF.sub.3                                                                            Cl                                                                              Cl  93-95                     286                                                                              NO.sub.2  H           C.sub.3 H.sub.7                                                                      Cl  H   CF.sub.3                                                                            Cl                                                                              Cl  71                        287                                                                              NO.sub.2  H           CH.sub.3                                                                             Cl  H   CF.sub.3                                                                            Cl                                                                              Cl 151                        288                                                                              NO.sub.2  H           C.sub.2 H.sub.5                                                                      Cl  H   CF.sub.3                                                                            Cl                                                                              Cl  91                        289                                                                              NO.sub.2  H           C.sub.4 H.sub.9                                                                      Cl  H   CF.sub.3                                                                            Cl                                                                              Cl  69                        290                                                                              NO.sub.2  CSC.sub.3 H.sub.7 -i                                                                      H      Cl  H   CF.sub.3                                                                            H Cl 122                        291                                                                              NO.sub.2  CSC.sub.3 H.sub.7                                                                         H      Cl  H   CF.sub.3                                                                            H Cl 119                        292                                                                              NO.sub.2  H           H      Cl  Cl  Cl    H H  125-33                     293                                                                              H         H           H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 155-57                     294                                                                              H         H           H      Cl  Cl  Cl    H Cl 105-09                     295                                                                              NO.sub.2  CON(CH.sub.3).sub.2                                                                       H      Cl  H   CF.sub.3                                                                            H Cl 105-15                     296                                                                              H         COCH.sub.3  H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 204-06                     297                                                                              NO.sub.2  COCH.sub.3  H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 163-66                     298                                                                              H         COCH.sub.3  H      Cl  Cl  Cl    H H   58-64                     299                                                                              H         COCH.sub.2 Cl                                                                             H      Cl  Cl  CF.sub.3                                                                            H Cl 115-18                     300                                                                              NO.sub.2  COCH.sub.3  H      Cl  Cl  Cl    H H   70-74                     301                                                                              NO.sub.2  COCH.sub.2 Cl                                                                             H      Cl  Cl  CF.sub.3                                                                            H Cl 144-48                     302                                                                              H         COCH.sub.2 Cl                                                                             H      Cl  H   SO.sub. 2 CF.sub.3                                                                  H Cl 122-24                     303                                                                              H         COCH(CH.sub.3).sub.2                                                                      H      Cl  H   CF.sub.3                                                                            H Cl .sup.1 H-NMR:                                                                 δ=6,56(1H, d)                                                           4-H in pyrazole ring       304                                                                              H         COCH(CH.sub.3).sub.2                                                                      H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 154-59                     305                                                                              H                                                                                        ##STR214## H      Cl  H   CF.sub.3                                                                            H Cl 161-65                     306                                                                              H         COC(CH.sub.3).sub.3                                                                       H      Cl  H   CF.sub.3                                                                            H Cl 175-79                     307                                                                              NO.sub.2  COCH.sub.2 Cl                                                                             H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 150-57                     308                                                                              NO.sub.2  COCH(CH.sub.3).sub.2                                                                      H      Cl  H   CF.sub.3                                                                            H Cl .sup.1 H-NMR:                                                                 δ=8,30(1H, s)                                                           3-H in pyrazole ring       309                                                                              NO.sub.2  COCH(CH.sub.3).sub.2                                                                      H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 159-60                     310                                                                              H         COCH(CH.sub.3).sub.2                                                                      H      Cl  Cl  CF.sub.3                                                                            H Cl  62-68                     311                                                                              H         COC.sub.3 H.sub.7 -n                                                                      H      Cl  Cl  CF.sub.3                                                                            H Cl 138-45                     312                                                                              NO.sub.2  COCH(CH.sub.3).sub.2                                                                      H      Cl  Cl  CF.sub.3                                                                            H Cl  98-106                    313                                                                              NO.sub.2  COC.sub.3 H.sub.7 -n                                                                      H      Cl  Cl  CF.sub.3                                                                            H Cl  85-92                     314                                                                              SCCl.sub.2 F                                                                            H           H      Cl  Cl  CF.sub.3                                                                            H Cl  60-65                     315                                                                              NO.sub.2                                                                                 ##STR215## H      Cl  H   CF.sub.3                                                                            H Cl  53-65                     316                                                                              NO.sub.2  COC(CH.sub.3).sub.3                                                                       H      Cl  H   CF.sub.3                                                                            H Cl 145-48                     317                                                                              H                                                                                        ##STR216## H      Cl  Cl  CF.sub.3                                                                            H Cl  58-62                     318                                                                              NO.sub.2  COCH(CH.sub.3).sub.2                                                                      H      Cl  H   SCF.sub.3                                                                           H Cl 110-18                     319                                                                              NO.sub.2                                                                                 ##STR217## H      Cl  Cl  CF.sub.3                                                                            H Cl 115-21                     320                                                                              SCCl.sub.2 F                                                                            H           H      Cl  Cl  Cl    H H   55-62                     321                                                                              SCCl.sub.2 F                                                                            H           H      CF.sub.3                                                                          H   Cl    H H  Oil                        322                                                                              SCCl.sub.2 F                                                                            H           H      Cl  H   CF.sub.3                                                                            H H   81-87                     323                                                                              SCCl.sub.2 F                                                                            H           H      Cl  H   OCF.sub.3                                                                           H H   77                        324                                                                              SCCl.sub.2 F                                                                            H           H      Cl  H   Cl    H H  Oil                        325                                                                              SCCl.sub.2 F                                                                            H           H      Cl  Cl  CF.sub.3                                                                            Cl                                                                              Cl  55-61                     326                                                                              H                                                                                        ##STR218## H      Cl  H   CF.sub.3                                                                            H Cl  58                        327                                                                              H         COC.sub.7 H.sub.15                                                                        H      Cl  H   CF.sub.3                                                                            H Cl 109-13                     328                                                                              H         COC(CH.sub.3).sub.3                                                                       H      Cl  Cl  CF.sub.3                                                                            H Cl 166-70                     329                                                                              H         COOCH.sub.3 H      Cl  Cl  CF.sub.3                                                                            H Cl  65-69                     330                                                                              H                                                                                        ##STR219## H      Cl  Cl  CF.sub.3                                                                            H Cl  65-69                     331                                                                              NO.sub.2  CONH.sub.2  H      Cl  H   CF.sub.3                                                                            H Cl 171-2                      332                                                                              NO.sub.2                                                                                 ##STR220## H      Cl  H   CF.sub.3                                                                            H Cl  97-107 (decomp.)          333                                                                              NO.sub.2  COC.sub.7 H.sub.15                                                                        H      Cl  H   CF.sub.3                                                                            H Cl  77-80                     334                                                                              NO.sub.2  COC(CH.sub.3).sub.3                                                                       H      Cl  Cl  CF.sub.3                                                                            H Cl 176-84                     335                                                                              NO.sub.2                                                                                 ##STR221## H      Cl  Cl  CF.sub.3                                                                            H Cl  60-67                     336                                                                              SCCl.sub.2 F                                                                            H           CH.sub.3                                                                             Cl  H   CF.sub.3                                                                            H Cl 107-10                     337                                                                              NO.sub.2  COOCH.sub.3 H      Cl  Cl  CF.sub.3                                                                            H Cl  75-81                     338                                                                              SCCl.sub.2 F                                                                            H           H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 148-53                     339                                                                              SCCl.sub.3                                                                              H           H      Cl  H   CF.sub.3                                                                            H Cl  75-88                     340                                                                              SCF.sub.3 H           H      Cl  H   CF.sub.3                                                                            H Cl  86-94                     341                                                                               ##STR222##                                                                             H           H      Cl  H   CF.sub.3                                                                            H Cl Oil                        342                                                                              SCCl.sub.2 F                                                                            H           H      Cl  H   SCF.sub.3                                                                           H Cl 104-17                     343                                                                              H                                                                                        ##STR223## H      Cl  H   CF.sub.3                                                                            H H  116-22                     344                                                                              NO.sub.2  COCH.sub.2 CH.sub.2 Cl                                                                    H      Cl  H   CF.sub.3                                                                            H H   50-55                     345                                                                              SOCCl.sub.2 F                                                                           H           H      Cl  H   Cl    H Cl  69-75                     346                                                                              SOCCl.sub.2 F                                                                           H           H      Cl  H   Cl    H Cl  63-69                     347                                                                              H                                                                                        ##STR224## H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 174-76                     348                                                                              H         COOCH.sub.3 H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl  62-66                     349                                                                              H         COCH.sub.2 CH.sub.2 Cl                                                                    H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 127-31                     350                                                                              SCCl.sub.2 F                                                                            H           H      Cl  H   OCF.sub.3                                                                           H Cl 101-7                      351                                                                              H         COCH.sub.2 CH.sub.2 Cl                                                                    H      Cl  Cl  CF.sub.3                                                                            H Cl 143-45                     352                                                                              NO.sub.2                                                                                 ##STR225## H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 147-52                     353                                                                              NO.sub.2  COCH.sub.2 CH.sub.2 Cl                                                                    H      Cl  H   SO.sub.2 CF.sub.                                                                    H Cl 111-14                     354                                                                              SCCl.sub.2 F                                                                            H           H      Cl  H   Cl    F CF.sub.3                                                                         Oil                        355                                                                              SCCl.sub.2 F                                                                            H           H      Br  H   CH(CH.sub.3).sub.2                                                                  H Br 130-135                    356                                                                              SO.sub.2CCl.sub.2 F                                                                     H           H      CF.sub.3                                                                          H   Cl    H H   61-65                     357                                                                              NO.sub.2  COOCH.sub.3 H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 166-69                     358                                                                              SO.sub.2CCl.sub.2 F                                                                     H           H      Cl  H   OCF.sub.3                                                                           H H  117-24                     359                                                                              SO.sub.2CCl.sub.2 F                                                                     H           H      Cl  H   CF.sub.3                                                                            H H  132-37                     360                                                                              SO.sub.2CF.sub.3                                                                        H           H      Cl  H   CF.sub.3                                                                            H Cl  57-63                     361                                                                              SO.sub.2CF.sub.3                                                                        H           H      Cl  H   CF.sub.3                                                                            H Cl  86-92                     362                                                                              SOCCl.sub.2 F                                                                           H           H      Cl  H   OCF.sub.3                                                                           H H   45-55                     363                                                                              NO.sub.2  COCH.sub.3  H      Cl  F   Cl    F Cl 147-57                     364                                                                              SCF.sub.2 CCl.sub.2 F                                                                   H           H      Cl  H   CF.sub.3                                                                            H Cl 117-19                     365                                                                              SCCl.sub.2 F                                                                            H           H      F   F   CF.sub. 3                                                                           F F                             366                                                                              NO.sub.2  COC.sub.2 H.sub.4 Cl                                                                      H      Cl  Cl  CF.sub.3                                                                            H Cl 130-33                     367                                                                              H         H           H      Cl  H   NO.sub.2                                                                            H H  189-91.5                   368                                                                              H         COC.sub.2 H.sub.5                                                                         H      Cl  H   NO.sub.2                                                                            H H   46-55                     369                                                                              H         COCH(CH.sub.3).sub.2                                                                      H      Cl  H   OCF.sub.3                                                                           H H   86-99                     370                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Cl  H   NO.sub.2                                                                            H H  108-13                     371                                                                              NO.sub.2  COCH(CH.sub.3).sub.2                                                                      H      Cl  H   OCF.sub.3                                                                           H H  115-19                     372                                                                              NO.sub.2  H           H      Cl  H   NO.sub.2                                                                            H H  157-62                     373                                                                              H         COCHClCH.sub.3                                                                            H      Cl  H   CF.sub.3                                                                            H Cl  55-57                     374                                                                              H         COCHClCH.sub.3                                                                            H      Cl  Cl  CF.sub.3                                                                            H Cl  53-55                     375                                                                              NO.sub.2  COCHClCH.sub.3                                                                            H      Cl  H   CF.sub.3                                                                            H Cl  53-56                     376                                                                              NO.sub.2  COCHClCH.sub.3                                                                            H      Cl  Cl  CF.sub.3                                                                            H Cl  50-52                     377                                                                              NO.sub.2  CON(CH.sub.3).sub.2                                                                       H      Cl  Cl  CF.sub.3                                                                            H Cl 163-66                     378                                                                              H         COCH.sub.2 SCH.sub.3                                                                      H      Cl  H   CF.sub.3                                                                            H Cl 124-6                      379                                                                              H         COCH.sub.2 SCH.sub.3                                                                      H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 121-3                      380                                                                              H         COCH.sub.2 SCH.sub.3                                                                      H      Cl  Cl  CF.sub.3                                                                            H Cl 138-40                     381                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Cl  H   CH.sub.3                                                                            H H   60-62                     382                                                                              NO.sub.2  H           H      Cl  H   CH.sub.3                                                                            H H   78-80                     383                                                                              H         COCCl.sub.3 H      Cl  H   CF.sub.3                                                                            H Cl 175-77                     384                                                                              H         COCCl.sub.3 H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 206-11                     385                                                                              H         COCCl.sub.3 H      Cl  Cl  CF.sub.3                                                                            H Cl 148-53                     386                                                                              H         COC.sub.2 H.sub.5                                                                         H      CH.sub.3                                                                          H   CH.sub.3                                                                            H CH.sub.3                                                                         113-7                      387                                                                              NO.sub.2  COCCl.sub.3 H      Cl  H   CF.sub.3                                                                            H Cl 167-70                     388                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      CH.sub.3                                                                          H   CH.sub.3                                                                            H CH.sub.3                                                                          49-56                     389                                                                              NO.sub.2  COCCl.sub.3 H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl 209-14                     390                                                                              NO.sub.2  COCCl.sub.3 H      Cl  Cl  CF.sub.3                                                                            H Cl 171-74                     391                                                                              Cl        H           H      Cl  H   CF.sub.3                                                                            H Cl 115-20                     392                                                                              H         COC.sub.4 H.sub.9                                                                         H      Cl  Cl  CF.sub.3                                                                            H Cl 130-4                      393                                                                              H                                                                                        ##STR226## H      Cl  Cl  CF.sub.3                                                                            H Cl 156-8                      394                                                                              H         COCH.sub.2 CH(CH.sub.3).sub.2                                                             H      Cl  Cl  CF.sub.3                                                                            H Cl 157-9                      395                                                                              H         COCH.sub.2 C(CH.sub.3).sub.3                                                              H      Cl  Cl  CF.sub.3                                                                            H Cl 170-5                      396                                                                              H                                                                                        ##STR227## H      Cl  Cl  CF.sub.3                                                                            H Cl 119-28                     397                                                                              NO.sub.2  COC.sub.4 H.sub.9                                                                         H      Cl  Cl  CF.sub.3                                                                            H Cl 120-28                     398                                                                              NO.sub.2                                                                                 ##STR228## H      Cl  Cl  CF.sub.3                                                                            H Cl 121-31                     399                                                                              NO.sub.2  COCH.sub.2 CH(CH.sub.3).sub.2                                                             H      Cl  Cl  CF.sub.3                                                                            H Cl  72-84                     400                                                                              NO.sub.2  COCH.sub.2 C(CH.sub.3).sub.3                                                              H      Cl  Cl  CF.sub.3                                                                            H Cl 153-58                     401                                                                              NO.sub.2  COCH(C.sub.2 H.sub.5).sub.2                                                               H      Cl  Cl  CF.sub.3                                                                            H Cl 152-56                     402                                                                              H         COC.sub.5 H.sub.11                                                                        H      Cl  H   CF.sub.3                                                                            H Cl  79-135                    403                                                                              H         COC.sub.5 H.sub.11                                                                        H      Cl  CF.sub.3                                                                          H     Cl                                                                              Cl  89-104                    404                                                                              H         COC.sub.7 H.sub.15                                                                        H      Cl  Cl  CF.sub.3                                                                            H Cl 117-26                     405                                                                              H         COCH.sub.2 OCH.sub.3                                                                      H      Cl  H   CF.sub.3                                                                            H Cl  99-102                    406                                                                              NO.sub.2  COC.sub.5 H.sub.11                                                                        H      Cl  H   CF.sub.3                                                                            H Cl  93-95                     407                                                                              NO.sub.2  COC.sub.5 H.sub.11                                                                        H      Cl  Cl  CF.sub.3                                                                            H Cl 100-3                      408                                                                              H         COCH.sub.2 OCH.sub.3                                                                      H      Cl  Cl  CF.sub.3                                                                            H Cl  38-45                     409                                                                              H         COCH.sub.2 OCH.sub.3                                                                      H      Cl  H   SO.sub.2 CF.sub.3                                                                   H Cl  97-101                    410                                                                              H                                                                                        ##STR229## H      Cl  Cl  CF.sub.3                                                                            H Cl 121-25                     411                                                                              H                                                                                        ##STR230## H      Cl  H   CF.sub.3                                                                            H H  Oil                        412                                                                              H                                                                                        ##STR231## H      Cl  H   SO.sub.2 CF.sub.2 Cl                                                                H Cl 140                        413                                                                              H         COCH.sub.2 OCH.sub.3                                                                      H      Cl  H   SO.sub.2 CF.sub.2 Cl                                                                H Cl 119-23                     414                                                                              NO.sub.2                                                                                 ##STR232## H      Cl  Cl  CF.sub.3                                                                            H Cl 115-20                     415                                                                              NO.sub.2                                                                                 ##STR233## H      Cl  H   CF.sub.3                                                                            H H  .sup.1 H-NMR:                                                                 δ=8,33(1H, s) 3H                                                        in pyrazole ring           416                                                                              NO.sub.2                                                                                 ##STR234## H      Cl  H   SO.sub.2 CF.sub.2 Cl                                                                H Cl 136                        417                                                                              H         COC.sub.2 H.sub.5                                                                         H      Cl  H   C(CH.sub.3).sub.3                                                                   H Cl 115- 19                    418                                                                              NO.sub.2  COCHCl.sub.2                                                                              H      Br  H   CH(CH.sub.3).sub.2                                                                  H Br  59-63                     419                                                                              H         COC.sub.2 H.sub.5                                                                         H      F   F   CF.sub.3                                                                            F Cl  53-57                     420                                                                              H         COC.sub.4 H.sub.9 -n                                                                      H      Cl  H   CF.sub.3                                                                            H H   82-84                     421                                                                              NO.sub.2  COCH.sub.2 OCH.sub.3                                                                      H      Cl  H   CF.sub.3                                                                            H Cl 119-20                     422                                                                              NO.sub.2  COCH.sub.2 OCH.sub.3                                                                      H      Cl  Cl  CF.sub.3                                                                            H Cl  92-97                     423                                                                              NO.sub.2  COCH.sub.2 OCH.sub.3                                                                      H      Cl  H   SOCF.sub.3                                                                          H Cl 121-26                     424                                                                              NO.sub.2  COCH.sub.2 OCH.sub.3                                                                      H      Cl  H   SO.sub.2 CClF.sub.2                                                                 H Cl 115-18                     425                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Cl  H   C(CH.sub.3).sub.3                                                                   H Cl 113-17                     426                                                                              SCH.sub.3 H           H      Cl  H   CF.sub.3                                                                            H Cl 106-08                     427                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      F   F   CF.sub.3                                                                            F Cl  93-99                     428                                                                              H         COC.sub.3 H.sub.7                                                                         H      Cl  H   CF.sub.3                                                                            H H   87-88                     429                                                                              H         COC.sub.3 H.sub.7                                                                         H      Cl  H   SO.sub.2 CF.sub.2 Cl                                                                H Cl 166-69                     430                                                                              H         COC.sub.3 H.sub.7                                                                         H      Cl  F   Cl    F Cl 165-67                     431                                                                              NO.sub.2  COC.sub.4 H.sub.9                                                                         H      Cl  H   CF.sub.3                                                                            H H   80-81                     432                                                                              NO.sub.2  H           H      Cl  H   C(CH.sub.3).sub.3                                                                   H Cl 179-85                     433                                                                              SO.sub.2CH.sub.3                                                                        H           H      Cl  H   Cl    H Cl 170-71                     434                                                                              SC.sub.6 H.sub.5                                                                        H           H      Cl  H   CF.sub.3                                                                            H Cl 124-27                     435                                                                              NO.sub.2  COC.sub.3 H.sub.7                                                                         H      Cl  H   CF.sub.3                                                                            H H  .sup.1 H-NMR:                                                                 δ=8,33                                                                  (1H, s), 3-H in                                                               pyrazole                                                                      ring                       436                                                                              NO.sub.2  COC.sub.3 H.sub.7                                                                         H      Cl  H   SO.sub.2 CF.sub.2 Cl                                                                H Cl 143-48                     437                                                                              NO.sub.2  COC.sub.3 H.sub.7                                                                         H      Cl  F   Cl    F Cl 115-18                     438                                                                              SCCl.sub.2 F                                                                            COCH.sub.3  H      Cl  H   CF.sub.3                                                                            H Cl 164-64                     439                                                                              SO.sub.2CCl.sub.2 F                                                                     COCH.sub.3  H      Cl  H   CF.sub.3                                                                            H Cl 156-64                     440                                                                              H         COCHCl.sub.2                                                                              H      Cl  F   CF.sub.3                                                                            H H  131-34                     441                                                                              SCH(CH.sub.3).sub.2                                                                     H           H      Cl  H   CF.sub.3                                                                            H Cl  77-79                     442                                                                              SC.sub.2 H.sub.5                                                                        H           H      Cl  H   CF.sub.3                                                                            H Cl  81-82                     443                                                                              H         H           H      H   F   CF.sub.3                                                                            H F   95-97                     444                                                                              NO.sub.2  COC.sub.6 H.sub.13                                                                        H      Cl  Cl  CF.sub.3                                                                            H Cl 104-06                     445                                                                              H         COCHCl.sub.2                                                                              H      F   F   F     F F   91-97                     446                                                                              H         COC.sub.2 H.sub.5                                                                         H      F   F   F     F F   92-96                     447                                                                              NO.sub.2  COC.sub.7 H.sub.15                                                                        H      Cl  Cl  CF.sub.3                                                                            H Cl  90-93                     448                                                                              NO.sub.2  COCHCl.sub.2                                                                              H      F   F   F     F F   43-53                     449                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      F   F   F     F F   90-92                     450                                                                              H         COCH.sub. 3 H      Cl  F   CF.sub.3                                                                            F Cl 162-63                     451                                                                              NO.sub.2  COCH.sub.3  H      Cl  F   CF.sub.3                                                                            F Cl 161-66                     452                                                                              SCCl.sub.2 F                                                                            H           C.sub.2 H.sub.5                                                                      Cl  H   CF.sub.3                                                                            H Cl .sup.1 H-NMR:                                                                 δ=7,75(1H, s)                                                           3H in pyrazole ring        453                                                                              NO.sub.2  H           H      F   F   F     F F  131-34                     454                                                                              SCF.sub.3 COCH.sub.3  COCH.sub.3                                                                           Cl  H   CF.sub.3                                                                            H Cl  63-68                     455                                                                              H         COCH.sub.3  H      Cl  Cl  CF.sub.3                                                                            Cl                                                                              Cl 209-13                     456                                                                              SCCl.sub.2 F                                                                            H           H      Cl  F   CF.sub.3                                                                            F Cl  81-87                     457                                                                              NO.sub.2  COCH.sub.3  H      Cl  Cl  CF.sub.3                                                                            Cl                                                                              Cl 156-59                     458                                                                              NO.sub.2  H           H      Cl  Cl  CF.sub.3                                                                            Cl                                                                              Cl 228-31                     459                                                                              H         COCH.sub.3  H      H   F   CF.sub.3                                                                            H F  109-11                     460                                                                              SCCl.sub.2 F                                                                            H           H      H   F   CF.sub.3                                                                            H F   48-55                     461                                                                              H         COCH.sub.3  CH.sub.3                                                                             Cl  H   CF.sub.3                                                                            H Cl 122-25                     462                                                                              SCCl.sub.2 F                                                                            H           H      Cl  H   Br    H Cl  92-94                     463                                                                              SCCl.sub.2 F                                                                            H           H      Cl  H   COOCH.sub.3                                                                         H Cl 140-44                     464                                                                              H         H           H      Br  H   CF.sub.3                                                                            H Br 112                        465                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Br  H   CF.sub.3                                                                            H Br 121                        466                                                                              SCCl.sub.2 F                                                                            H           H      Br  H   CF.sub.3                                                                            H Br  80-85                     467                                                                              SCCl.sub.2 F                                                                            H           H      Cl  H   F     H H   68-72                     468                                                                              SO.sub.2CCl.sub.2 F                                                                     H           H      Br  H   CF.sub.3                                                                            H Br 101-06                     469                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Cl  H   F     H H  1H-NMR:                                                                       δ=1,08(3H,                                                              t), 2,38(2H, q);                                                              824(1H, s)                 470                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      F   H   Cl    H H  110-13                     471                                                                              SCCl.sub.2 F                                                                            H           H      F   H   Cl    H H   64-68                     472                                                                              NO.sub.2  H           H      Br  H   CF.sub.3                                                                            H Br 185                        473                                                                              SCCl.sub.2 F                                                                            H           H      Cl  CF.sub.3                                                                          Cl    H H                             474                                                                              SO.sub.2CCl.sub.2 F                                                                     H           H      Cl  H   Br    H Cl 100-04                     475                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Cl  H   CF.sub.3                                                                            H Cl 115-18                     476                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Br  H   F     H Br 160                        477                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Br  H   CF.sub.3                                                                            H H   45-55                     478                                                                              NO.sub.2  H           H      Br  H   F     H Br 193                        479                                                                              NO.sub.2  H           H      Br  H   CF.sub.3                                                                            H H  ca. 90                     480                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      OCF.sub.3                                                                         H   Br    H Br 105-110                    481                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Cl  H   CF.sub.3                                                                            H Br  98                        482                                                                              NO.sub.2  H           H      Br  H   CF.sub.3                                                                            H Cl 203                        483                                                                              NO.sub.2  H           H      OCF.sub.3                                                                         H   Br    H Br 102-06                     484                                                                              NO.sub.2  COCH.sub.3  H      Cl  H   CF.sub.3                                                                            H Br 133-42                     485                                                                              NO.sub.2  COCH.sub.2 Cl                                                                             H      Cl  H   CF.sub. 3                                                                           H Br 137-41                     486                                                                              H         H           H      OCF.sub.3                                                                         H   Cl    H H   78                        487                                                                              NO.sub.2  COCH.sub.3  H      CH.sub.3                                                                          H   Br    H CH.sub.3                                                                          63-68                     488                                                                              NO.sub.2  H           C.sub.2 H.sub.5                                                                      Cl  H   CF.sub.3                                                                            H Br 105-12                     489                                                                              NO.sub.2  H           H      CH.sub.3                                                                          H   Br    H CH.sub.3                                                                         145-68                     490                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Br  H   F     H Cl 133-35                     491                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      Br  H   Br    H F   50-70                     492                                                                              NO.sub.2  H           H      Br  H   Br    H F  141                        493                                                                              NO.sub.2                                                                                 ##STR235## H      Cl  H   CF.sub.3                                                                            H Cl 116-19                     494                                                                              NO.sub.2                                                                                 ##STR236## H      Br  H   CF.sub.3                                                                            H H   99-104                    495                                                                              NO.sub.2  COCH.sub.3  H      Br  H   CF.sub.3                                                                            H H  110-17                     496                                                                              NO.sub.2  COCH(CH.sub.3).sub.2                                                                      H      Br  H   CF.sub.3                                                                            H H  140-44                     497                                                                              NO.sub.2  COC.sub.2 H.sub.5                                                                         H      F   H   Cl    H Br  75                        498                                                                              H         COC.sub.2 H.sub.5                                                                         H      Br  Cl  CH.sub.3                                                                            H Br 211-219                    499                                                                              NO.sub.2  H           CH(CH.sub.3).sub.2                                                                   Cl  H   CF.sub.3                                                                            H Cl 170-73                     500                                                                              NO.sub.2  COCH.sub.3  H      Br  Cl  CH.sub.3                                                                            H Br  90-116                    501                                                                              NO.sub.2  H           H      Br  Cl  CH.sub.3                                                                            H Br 110-72                     502                                                                              NO.sub.2  H           H      F   H   Cl    H Br 157                        503                                                                              SO.sub.2CH.sub.3                                                                        H           H      Cl  H   CF.sub.3                                                                            H Cl  60-65                     504                                                                              NO.sub.2  COCF.sub.3  H      Br  H   CF.sub.3                                                                            H H  .sup.1 H-NMR:                                                                 δ=7,98(1H,                                                              s), 8,38(2H, s);                                                              9,48(1H, s)                505                                                                              NO.sub.2  CHO         H      Cl  Cl  CF.sub.3                                                                            H Cl 142-148                    __________________________________________________________________________

Use Examples

The compound listed below is used as a comparative substance in the useexamples which follow: ##STR237##4-Cyano-5-propionamido-1-(2,4,6-trichlorophenyl)-pyrazole (disclosed inU.S. Pat. Nos. 4,459,150 and 4,496,390).

Example A Pre-emergence Test

Solvent: 5 parts by weight of acetone.

Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive. Afterthree weeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction

In this test, for example, the compound according to preparation Example3 is clearly superior to the prior art, both in herbicidal activity andin selectivity with respect to crop plants.

Example B Post-Emergence Test

Solvent: 5 parts by weight of acetone.

Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amounts of active compound desired per unit area. Theconcentration of the spray liquor is so chosen that the particularamounts of active compound desired are applied in 2,000 l of water/ha.After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control. Thefigures denote:

0%=no action (like untreated control)

100%=total destruction

In this test, for example, the compound according to preparation Example3 is clearly superior to the prior art, both in herbicidal activity andin selectivity with respect to crop plants.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

What is claimed is:
 1. A 5-amino-1-phenyl-pyrazole of the formula##STR238## in which R¹ represents nitro,R² represents hydrogen, R³independently of R² represents hydrogen or alkyl having up to 4 carbonatoms, R⁴ and R⁶ independently of one another represent cyano, nitro,halogen, alkyl having up to 4 carbon atoms, alkoxy having up to 4 carbonatoms, alkoxy carbonyl having up to 4 carbon atoms, halogenoalkyl havingup to 4 carbon atoms, halogenoalkoxy having up to 4 carbon atoms or aradical --S(O)_(n) --R¹³ and R⁵, R⁷ and R⁸ independently of one anotherand of R⁴ and R⁶ represent the same radicals as R⁴ and R⁶ andadditionally represent hydrogen and R¹³ represents alkyl having up to 4carbon atoms, halogenoalkyl having up to 4 carbon atoms, amino,alkylamino having up to 4 carbon atoms or dialkylamino having up to 4carbon atoms in the individual alkyl parts, and n represents the numbers0, 1 or
 2. 2. A 5-amino-1-phenyl-pyrazole according to claim 1,whereinR¹ represents nitro, halogen, alkyl or halogenoalkyl, each ofwhich is straight-chain or branched and each of which has up to 6 carbonatoms, said halogenoalkyl having up to 9 identical or different halogenatoms, or represents phenyl which is optionally monosubstituted orpolysubstituted by identical or different substituents selected from thegroup consisting of halogen, nitro, alkyl, alkoxy and halogenoalkyl,each having up to 4 carbon atoms, or represents one of the radicals##STR239## R² represents hydrogen, R³ independently of R² representshydrogen or straight-chain or branched alkyl having up to 4 carbonatoms, R⁴ and R⁶ independently of one another represent cyano, nitro,halogen, or alkyl, alkoxy, alkoxy carbonyl, each of which isstraight-chain or branched and each of which has up to 4 carbon atoms,and furthermore represents halogenoalkyl or halogenoalkoxy, each ofwhich being straight-chain or branched and each of which has up to 4carbon atoms and up to 9 identical or different halogen atoms, orrepresents a radical --S(O)_(n) --R¹³, and R⁵, R⁷ and R⁸ independentlyof one another and of R⁴ and R⁶ represent the same radicals as R⁴ and R⁶and additionally represent hydrogen and R¹³ represents amino, and alkyl,alkylamino dialkylamino or halogenalkyl, each of which beingstraight-chain or branched and each of which having up to 4 carbon atomsin the individual alkyl parts and, said halogenoalkyl having up to 9identical or different halogen atoms, and n represents the numbers 0, 1or
 2. 3. An 5-amino-1-phenyl-pyraxole having a formula selected from thegroup consisting of ##STR240##
 4. A herbicidal composition comprising aherbicidally effective amount of a compound according to claim 1 inadmixture with a diluent.
 5. A herbicidal composition, comprising aherbicidally effective amount of a compound in admixture with a diluent,wherein said compound is selected from the group consisting of##STR241##